JP7363171B2 - Manufacturing method of polyester resin - Google Patents

Description

The present invention relates to a method for producing a polyester resin in which a desired organic group can be introduced into a side chain.

Conventionally, synthetic resins have been widely used as resins for various base materials because they have excellent properties such as dimensional stability, mechanical properties, heat resistance, transparency, electrical properties, and chemical resistance. For example, polyester films are used in various industrial fields such as packaging materials, magnetic cards, and printing materials.
In addition, polyester resins are used as compositions such as coating compositions, primer compositions, pressure-sensitive adhesive compositions, adhesive compositions, etc. In particular, when this composition is coated on a polyester film, polyester resin It is useful in terms of adhesion to the film.
In such a case, it is conceivable to further introduce a functional structural moiety into the main chain or side chain of a general polyester resin.
For example, it has been proposed to introduce a structural site of an ethylenically unsaturated group into a polyester resin by reacting an acrylic monomer having a glycidyl group with a polyester resin having a carboxyl group (for example, Patent Document 1 reference).

Japanese Patent Application Publication No. 2011-122020

However, in the disclosed method of Patent Document 1, (1) it is necessary to use a monomer having a glycidyl group, which limits the compounds that can be introduced, and (2) the reactivity of glycidyl groups and carboxyl groups is low, so depending on the system, There are concerns that sufficient reaction may not be obtained, or that it is necessary to carry out the reaction at a higher temperature for a longer time to increase the reaction rate, which may cause cleavage of functional groups such as unsaturated groups, resulting in gelation. (3) As a result of the reaction between the glycidyl group and the carboxy group, hydroxyl groups are generated, resulting in problems such as a decrease in water resistance of the resulting polymer, and further improvements are required.

Therefore, the present invention aims to provide a method for producing a polyester resin that can introduce a desired structural site, such as an unsaturated group, into the side chain of the polyester resin. This is the purpose.

In view of the above circumstances, the present inventor has conducted intensive research and found that in the presence of a specific compound (C) and a basic compound (D) containing a Group 15 element, a polyester resin having a carboxy group in the side chain ( The present invention was completed by discovering that a desired structural moiety can be efficiently added to the side chain of a polyester resin by reacting A) with an active hydrogen group-containing compound (B).

That is, the present invention combines a polyester resin (A) having a carboxyl group in the side chain and an active hydrogen group-containing compound (B) with a compound (C) represented by the following general formula (1) and a Group 15 element. The gist thereof is a method for producing a polyester resin, which is reacted in the presence of a basic compound (D) having the following.

According to the production method of the present invention, the polyester resin (A) having a carboxyl group in the side chain and the active hydrogen group-containing compound (B) are combined with the compound (C) represented by the above general formula (1) and the group 15 compound. Since the reaction is carried out in the presence of the basic compound (D) having the element, it is possible to efficiently obtain a polyester resin into which a desired structural moiety is introduced.
Furthermore, if the structural part to be introduced has a functional structural part, for example an ethylenically unsaturated group, a coating layer, in particular a prism layer, is provided on the polyester resin substrate, such as a polyester film. It can be suitably used as a polyester resin to form a primer composition for.

Hereinafter, the present invention will be explained in detail, but these are examples of desirable embodiments.
In the present invention, the term "carboxylic acid" includes carboxylic acid salts, carboxylic acid anhydrides, carboxylic acid halides, carboxylic esters, and the like.
In the present invention, the term "sheet" conceptually includes sheets, films, and tapes.

Moreover, in the present invention, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group.
Furthermore, in the present invention, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acryloyl" means acryloyl or methacryloyl. Moreover, "(meth)acrylate" means acrylate or methacrylate.

The production method of the present invention comprises a polyester resin (A) having a carboxyl group in its side chain (hereinafter sometimes simply referred to as "polyester resin (A)") and an active hydrogen group-containing compound (B). The reaction is carried out in the presence of a compound (C) represented by the following general formula (1) and a basic compound (D) having a Group 15 element, and a polyester resin into which a desired structural moiety is introduced by this reaction. is obtained.
Components (A) to (D) used in the method for producing a polyester resin of the present invention will be explained in order below.

[Polyester resin (A) having a carboxyl group in the side chain]
The polyester resin (A) is usually obtained by copolymerizing a copolymer component containing a polyhydric carboxylic acid (a1) and a polyol (a2) as constituent raw materials. The polyester resin (A) has a carboxy group in the side chain, and such polyester resin (A) has a carboxylic acid anhydride structure as the polycarboxylic acid (a1). It can be obtained by using a carboxylic anhydride (hereinafter sometimes simply referred to as "polycarboxylic anhydride").

[Polycarboxylic acid (a1)]
Examples of the polyvalent carboxylic acid (a1) used as a constituent raw material of the polyester resin (A) include divalent carboxylic acids, trivalent or higher polyvalent carboxylic acids, and the like. Among these, dihydric carboxylic acids are preferred as the polycarboxylic acid (a1) constituting the main chain of the polyester resin (A).

Examples of the above-mentioned dihydric carboxylic acids include:
Malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, thiodipropionic acid , diglycolic acid, aliphatic dicarboxylic acids such as 1,9-nonanedicarboxylic acid;
Phthalic acid, terephthalic acid, isophthalic acid, benzylmalonic acid, diphenic acid, 4,4'-oxydibenzoic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acids such as naphthalene dicarboxylic acid;
Alicyclic groups such as 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, adamantanedicarboxylic acid, etc. dicarboxylic acid;
etc. These can be used alone or in combination of two or more, and are appropriately selected depending on desired physical properties.

Among these, when the polyester resin obtained by the production method of the present invention is used for a primer layer (primer composition) for improving the adhesion between the polyester resin base material and the coating layer, the adhesion with the coating layer is It is preferable to use at least one of an aromatic dicarboxylic acid and an alicyclic dicarboxylic acid as a main component, since it has excellent stability of an aqueous liquid when dissolved or dispersed in an aqueous solvent, and particularly for adhesion. From the standpoint of superiority, it is preferable to use aromatic dicarboxylic acids as the main component, and more preferably to use isophthalic acid as the main component.
Here, the term "main component" means that the content is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, based on the entire polyhydric carboxylic acid (a1).

The content of the dicarboxylic acid is preferably 70 to 98 mol%, particularly 75 to 97 mol%, more preferably 80 to 96 mol%, particularly is preferably 85 to 95 mol%. If this content rate is too low, there is a tendency for the moisture and heat resistance to decrease or gelation occurs during the manufacturing process, and if this content rate is too high, the amount of active hydrogen group-containing compound (B) that can be introduced tends to decrease. There is.

Furthermore, a polyhydric carboxylic acid having a valence of 3 or more can be used for the purpose of increasing the number of branch points in the polyester resin (A).
Examples of the trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, adamantanetricarboxylic acid, trimesic acid, and the like. These can be used alone or in combination of two or more.

The polyester resin (A) used in the present invention contains a polyvalent carboxylic acid anhydride as the polyvalent carboxylic acid (a1), and the polyvalent carboxylic acid anhydride introduces a carboxy group into the side chain. For the purpose, it is preferable to have at least two carboxylic acid anhydride structures, for example,
1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic anhydride), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, ethylene glycol bistrimelitate dianhydride, 2,2',3,3' - Aromatic polyvalent carboxyls such as diphenyltetracarboxylic dianhydride, 2,2',3,3'-diphenylsulfonetetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, etc. Acid anhydride;
1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 5-(2 , 5-dioxotetrahydrofuryl)-3-cyclohexene-1,2-dicarboxylic acid anhydride, alicyclic polyvalent carboxylic acid anhydride such as cyclopentanetetracarboxylic dianhydride;
Aliphatic polyhydric carboxylic acid anhydrides such as ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and 1,2,3,4-pentanetetracarboxylic dianhydride;
etc. These can be used alone or in combination of two or more.

Among these polycarboxylic acid anhydrides, aliphatic polycarboxylic acid anhydrides and alicyclic polycarboxylic acid anhydrides are preferable because of their excellent reactivity with the active hydrogen group-containing compound (B) described below. more preferably alicyclic polycarboxylic acid anhydride, particularly preferably 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride It is a thing.

The content of the polycarboxylic anhydride in the polycarboxylic acid (a1) is preferably 2 to 30 mol%, particularly 3 to 25 mol%, based on the entire polycarboxylic acid (a1). Further, it is preferably 4 to 20 mol%, particularly 5 to 15 mol%. If this content ratio is too low, the amount of active hydrogen group-containing compound (B) that can be introduced tends to decrease. If this content ratio is too high, there is a tendency for gelation to occur during the manufacturing process or for a decrease in heat and humidity resistance.

[Polyol (a2)]
Examples of the polyol (a2) include dihydric alcohols, trivalent or higher polyhydric alcohols, and the like.

Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9- Aliphatic diols with a linear structure such as nonanediol, 1,10-decanediol, 1,12-dodecanediol, polyethylene glycol, polytetramethylene glycol;
Propylene glycol, dipropylene glycol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 3-methyl-1,5-pentanediol , aliphatic diols having a branched structure such as 2,2,4-trimethyl-1,6-hexanediol;
1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, spiroglycol, tricyclodecanedimethanol, adamantanediol, 2,2,4,4-tetramethyl-1,3 -Alicyclic diols such as cyclobutanediol;
4,4'-thiodiphenol, 4,4'-methylene diphenol, bisphenol S, bisphenol A, bisphenol fluorene, 4,4'-dihydroxybiphenyl, o-, m- and p-dihydroxybenzene, 2,5- Aromatic diols such as naphthalene diol and p-xylene diol;
and ethylene oxide and propylene oxide adducts thereof;
etc. These can be used alone or in combination of two or more.

Examples of the trihydric or higher polyhydric alcohol include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol, adamantanetriol, and the like. These can be used alone or in combination of two or more.

These polyols (a2) can be used alone or in combination of two or more, and are appropriately selected according to desired physical properties.

Among these, when the polyester resin obtained by the production method of the present invention is used for the above-mentioned primer layer (primer composition), dihydric alcohol is preferable, and more preferably, from the viewpoint of adhesion between the coating layer and the primer layer. It is an aliphatic diol with a straight chain structure, more preferably an aliphatic diol with a straight chain structure other than ethylene glycol because it has moderate flexibility and excellent adhesion, and particularly preferably diethylene glycol, 1 , 4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, and diethylene glycol is particularly preferred since it lowers the crystallinity of the resin and provides better adhesion.

In addition, when using the polyester resin obtained by the production method of the present invention for the primer layer (primer composition), from the viewpoint of stability of the aqueous liquid when dissolved or dispersed in an aqueous solvent, it is necessary to have a linear structure. It is preferable to use aliphatic diols with other polyols in combination with other polyols, and furthermore, from the viewpoint of adhesion between the coating layer and the primer layer, aliphatic diols with a linear structure and aliphatic polyols with a branched structure are used in combination. It is preferable. The aliphatic polyol having a branched structure is preferably neopentyl glycol, 2-methyl-1,3-propanediol, or butylethylpropanediol, and particularly preferably neopentyl glycol.

When a linear aliphatic diol and other polyols are used together, the mixing ratio (mole ratio) of the linear aliphatic diol and other polyol is the linear aliphatic diol/ Other polyols are preferably from 98/2 to 50/50, more preferably from 95/5 to 60/40, and particularly preferably from 90/10 to 70/30.
If the amount of polyol components other than linear aliphatic diols is too large, the adhesion tends to decrease, and if it is too small, the stability of the aqueous liquid tends to decrease.

[Method for producing polyester resin (A)]
The polyester resin (A) can be obtained by appropriately selecting the polycarboxylic acid (a1) and the polyol (a2) according to desired physical properties and copolymerizing them. In particular, production by a method in which a polycarboxylic anhydride is reacted with a hydroxyl group-containing prepolymer obtained by copolymerizing a polycarboxylic acid (a1) excluding a polycarboxylic acid anhydride and a polyol (a2). is preferred.
The method for producing the polyester resin (A) will be described in detail below.

First, a predetermined amount of polycarboxylic acid (a1) excluding polycarboxylic acid anhydride and polyol (a2) are mixed. At this time, the mixing ratio (molar ratio) of the carboxy group of the polycarboxylic acid (a1) excluding the polycarboxylic acid anhydride and the hydroxyl group of the polyol (a2) is 1 mole of the carboxyl group of the polycarboxylic acid (a1). The amount of hydroxyl groups in polyol (a2) is preferably 1.02 to 1.3 mol, more preferably 1.03 to 1.2 mol, particularly preferably 1.04 to 1.15 mol. .

This mixture is charged into an appropriate reactor and heated to usually 170 to 270°C to proceed with the esterification reaction or transesterification reaction while distilling off the by-product water or methanol. Produces polymers.

In the above-mentioned esterification reaction or transesterification reaction, a catalyst is usually used, and specifically, for example, a titanium-based catalyst such as tetraisopropyl titanate or tetrabutyl titanate, an antimony-based catalyst such as antimony trioxide, germanium dioxide, etc. Examples include catalysts such as germanium-based catalysts, zinc acetate, manganese acetate, dibutyltin oxide, etc., and one or more of these may be used. Among these, antimony trioxide, tetrabutyl titanate, germanium dioxide, and zinc acetate are preferred from the viewpoint of high catalytic activity and hue balance.

The amount of the catalyst blended is preferably 1 to 10,000 ppm, particularly preferably 10 to 5,000 ppm, and even more preferably 20 to 3,000 ppm, based on the mixture charged in the reaction vessel. If the amount is too small, the reaction tends to be difficult to proceed sufficiently, and if it is too large, there is no advantage such as shortening the reaction time, and side reactions tend to occur.

A polyester resin (A) can be obtained by subjecting the obtained hydroxyl group-containing prepolymer to a ring-opening addition reaction with a polyhydric carboxylic acid anhydride.

When reacting the above hydroxyl group-containing prepolymer with a polyvalent carboxylic acid anhydride, the molar ratio of the number of moles of acid anhydride groups in the polyvalent carboxylic acid anhydride to the number of moles of hydroxyl groups in the hydroxyl group-containing prepolymer (polyvalent The ratio (number of moles of acid anhydride groups in carboxylic acid anhydride/number of moles of hydroxyl groups in hydroxyl group-containing prepolymer) is preferably 0.8 to 1.8, more preferably 0.9 to 1.5, particularly It is preferable to set it to 1.0 to 1.2. Under the above reaction conditions, the hydroxyl group-containing prepolymer is chain-extended and has a carboxy group in its side chain. Therefore, it becomes easier to adjust the weight average molecular weight of the polyester resin (A) to the range described below, and various physical properties such as adhesion to substrates, adhesion to adherends, moist heat resistance, and solvent resistance are improved. Tend. Moreover, since the amount of remaining hydroxyl groups is suppressed, problems such as gelation are less likely to occur in the reaction for introducing the active hydrogen group-containing compound (B), which will be described later.

It is preferable to use a catalyst in the reaction between the hydroxyl group-containing prepolymer and the polycarboxylic anhydride. Although the catalyst is not particularly limited, amine catalysts are preferred, and triethylamine is particularly preferred since it easily evaporates during the drying process.

In addition, the reaction temperature is usually room temperature (23°C) to 100°C, preferably 40 to 90°C when a catalyst is used, and usually 230°C or less, preferably 150 to 210°C when a catalyst is not used. , particularly preferably 160 to 190°C.

A solvent is not necessarily required in the above reaction, but if the viscosity of the reactant at the above temperature is too high, an appropriate solvent may be used to facilitate stirring.

Examples of the above-mentioned solvents include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic solvents such as benzene, toluene, xylene, mesitylene, and pseudocumene, and amide solvents such as dimethylformamide and dimethylacetamide. . Note that it is preferable not to use solvents that may react with the polyester resin, such as ester solvents and alcohol solvents.

Furthermore, when producing the polyester resin (A), various additives such as stabilizers may be used as appropriate.

Thus, the polyester resin (A) is obtained by the method described above.
The polyester resin (A) has a carboxyl group in its side chain, and the carboxy group has excellent reactivity with the active hydrogen group-containing compound (B). It is preferably derived from at least one polycarboxylic acid selected from cyclic polycarboxylic acids, and at least one polycarboxylic acid anhydride selected from aliphatic polycarboxylic anhydrides and alicyclic polycarboxylic anhydrides. 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1 , 2-dicarboxylic acid anhydride is particularly preferred.

The hydroxyl value of the polyester resin (A) is usually 10 mgKOH/g or less, preferably 8 mgKOH/g or less, particularly It is preferably 5 mgKOH/g or less, particularly preferably 1 mgKOH/g or less. In addition, the smaller the hydroxyl value, the better, and the lower limit is 0 mgKOH/g. In the present invention, the hydroxyl value is determined by neutralization titration based on JIS K0070.

Further, the acid value of the polyester resin (A) is usually 4 to 100 mgKOH/g, preferably 10 to 80 mgKOH/g, particularly preferably 20 to 60 mgKOH/g. If the acid value is too low, there will be fewer reaction points for introducing the active hydrogen group-containing compound (B), which will be described later, and the amount of the active hydrogen group-containing compound (B) to be introduced will tend to decrease. On the other hand, if the acid value is too high, the heat and humidity resistance tends to decrease. In the present invention, the acid value is determined by neutralization titration based on JIS K0070.

Note that the "acid value" in the present invention is due to the content of carboxy groups contained in the polyester resin (A). Furthermore, the term "carboxy group" in the present invention includes a carboxylate ion state in which the carboxy group is neutralized with a basic compound.

The weight average molecular weight of the polyester resin (A) is usually 2,000 to 100,000, preferably 5,000 to 50,000, more preferably 8,000 to 40,000, particularly preferably 10,000 to 30,000. If the weight average molecular weight is too small, physical properties such as adhesion to substrates, adhesion to adherends, heat and humidity resistance, and solvent resistance tend to deteriorate, while if the weight average molecular weight is too large, adhesion and Adhesion, solvent solubility, water dispersibility, handling properties, etc. tend to decrease.

The peak top molecular weight of the polyester resin (A) is preferably 2,000 to 60,000, more preferably 5,000 to 40,000, even more preferably 7,000 to 30,000, and particularly preferably 10,000 to 25,000. If the peak top molecular weight is too small, physical properties such as adhesion to substrates, adhesion to adherends, moist heat resistance, and solvent resistance tend to decrease. On the other hand, if the peak top molecular weight is too large, solvent solubility, water dispersibility, and handling properties tend to decrease.

In the present invention, the weight average molecular weight and peak top molecular weight are molecular weights calculated in terms of standard polystyrene molecular weight. Molecular weight: 2×10 ⁶ , number of theoretical plates: 16,000 plates/piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 4 μm) is measured by using two pieces in series.

The glass transition temperature (Tg) of the polyester resin (A) is usually -70 to 150°C, preferably -50 to 100°C, particularly preferably -20 to 80°C, and even more preferably 0 to 60°C. be.

In the present invention, the glass transition temperature is a value obtained by measuring using a differential scanning calorimeter, and the measurement conditions vary depending on the structure of the polyester resin to be measured, but for example, the measurement temperature range is -90 to 100°C. , the temperature increase rate is 10°C/min.

[Active hydrogen group-containing compound (B)]
In the production method of the present invention, the structure derived from the active hydrogen group-containing compound (B) is produced by reacting the active hydrogen group of the active hydrogen group-containing compound (B) with the carboxy group of the polyester resin (A). A moiety is introduced into the side chain of the polyester resin.

The number of active hydrogen groups that the active hydrogen group-containing compound (B) has is not particularly limited, but from the viewpoint of reactivity with the polyester resin (A), one is preferable.
Examples of the active hydrogen group include an amino group, a mercapto group, a hydroxyl group, etc. Among them, an amino group, a mercapto group, and a hydroxyl group are preferred, an amino group and a hydroxyl group are particularly preferred, and a hydroxyl group is particularly preferred.

In addition, the active hydrogen group-containing compound (B) is not particularly limited in other structures as long as it has an active hydrogen group, but from the viewpoint of imparting various functionalities to the resulting polyester resin, functional groups may be added. It is preferable to have a functional group, and it is particularly preferable to have a functional group at the terminal of the active hydrogen group-containing compound (B). Further, the active hydrogen group-containing compound (B) may be a polymer such as a polymer or an oligomer.

Examples of the above-mentioned functional groups include epoxy groups and unsaturated groups. The number of functional groups that the active hydrogen group-containing compound (B) has is not particularly limited, but it has at least one functional group in the molecule, and if various functions are considered, it has two or more functional groups in the molecule. It is also preferable. Moreover, the above-mentioned functional groups may be used alone or in combination of two or more kinds.

The above-mentioned functional group can be appropriately selected according to the desired functionality of the polyester resin. For example, when the polyester resin obtained in the present invention is used for a primer layer (primer composition) for improving the adhesion between a polyester film base material and a coating layer, especially a prism layer, the prism layer is formed. The functional group capable of reacting with the carbon-carbon double bond in the composition preferably has an unsaturated group, particularly an ethylenically unsaturated group.

Examples of the ethylenically unsaturated group include a vinyl group, a vinyl ether group, a vinyl ester group, and a (meth)acryloyl group. Among these, from the viewpoint of reactivity (adhesion) between the coating layer and the primer layer, a (meth)acryloyl group is preferred, and an acryloyl group is particularly preferred.

Among these, it is preferable that the active hydrogen group-containing compound (B) is an active hydrogen group-containing (meth)acrylate, from the viewpoint of excellent adhesion between the coating layer and the primer layer; Acrylates are particularly preferred.
Examples of the hydroxyl group-containing (meth)acrylates include monofunctional hydroxyl group-containing (meth)acrylates and polyfunctional hydroxyl group-containing (meth)acrylates.

Examples of the monofunctional hydroxyl group-containing (meth)acrylate include polyalkylene glycol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Examples include 4-hydroxybutyl (meth)acrylate, ethylene glycol-propylene glycol block copolymer mono(meth)acrylate, and ethylene glycol-tetramethylene glycol copolymer mono(meth)acrylate. These can be used alone or in combination of two or more.

Examples of the polyfunctional hydroxyl group-containing (meth)acrylate include trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like. These can be used alone or in combination of two or more.

Among these hydroxyl group-containing (meth)acrylates, from the viewpoint of adhesion between the coating layer and the primer layer, monofunctional hydroxyl group-containing (meth)acrylates are preferred, and polyalkylene glycol mono(meth)acrylates are more preferred.

The number average molecular weight of the polyalkylene glycol mono(meth)acrylate is usually 100 to 1000, preferably 110 to 800, more preferably 120 to 500. When the number average molecular weight is within the above range, the (meth)acryloyl group concentration becomes high, so the adhesion between the coating layer and the primer layer tends to be excellent. Note that the number average molecular weight of the polyalkylene glycol mono(meth)acrylate can be calculated based on the hydroxyl value measured in accordance with JIS K 1557-1.

Specific examples of the polyalkylene glycol mono(meth)acrylate include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, and the like. Among these, from the viewpoint of reactivity with carboxyl groups, those having a primary hydroxyl group (for example, polyethylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, etc.) are preferable, and are suitable for coating layers and primer layers. In terms of adhesion, polyethylene glycol mono(meth)acrylate is preferred, and polyethylene glycol monoacrylate is particularly preferred.

The amount of active hydrogen group-containing compound (B) used in the method for producing polyester resin of the present invention is as follows: The amount of active hydrogen groups it has is usually 10 to 150 mol%, preferably 15 to 100 mol%, particularly preferably 20 to 90 mol%. If the amount of the active hydrogen group-containing compound (B) used is too small, the number of structural sites introduced into the side chains of the polyester resin (A) tends to decrease, and the amount of the active hydrogen group-containing compound (B) used becomes too small. If the amount is too large, the excess active hydrogen group-containing compound (B) tends to bleed out.

[Compound (C) represented by general formula (1)]
The method for producing a polyester resin of the present invention is carried out in the presence of a compound (C) represented by the following general formula (1) [hereinafter sometimes simply referred to as "compound (C)"]. .

In the above general formula (1) representing compound (C), R ¹ and R ² each represent a hydrocarbon group. Further, the number of carbon atoms in the hydrocarbon group is from 1 to 20, preferably from 2 to 10, particularly preferably from 3 to 7, from the viewpoint of availability.

The type and structure of R ¹ and R ² are not limited as long as they are hydrocarbon groups. Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and the like. These may have any linear, branched, or cyclic structure. Moreover, an aryl group is also mentioned as the said hydrocarbon group. Furthermore, these hydrocarbon groups may contain an ether bond in their structure, or R ¹ and R ² may be bonded to form a cyclic structure.

Specific examples of the above compound (C) include diallyl dicarbonate, di-t-butyl dicarbonate, di-t-amyl dicarbonate, and dibenzyl dicarbonate. Among these, di-t-butyl dicarbonate, in which R ¹ and R ² are t-butyl groups, is preferred because it can efficiently produce a polyester resin into which a desired structural moiety has been introduced.

As the compound (C), commercially available compounds can be used, but compounds produced by known methods may also be used. Further, the compound (C) may be used alone or in combination of two or more kinds.
In addition, although the compound (C) produces an intermediate containing components derived from the compound by reaction, the polyester resin finally obtained does not contain components derived from the compound (C).

Further, the amount of compound (C) used in the method for producing a polyester resin of the present invention is usually 0.8 to 5 equivalents, preferably 0.8 to 5 equivalents, based on the active hydrogen group possessed by the active hydrogen group-containing compound (B). The amount is 0.9 to 3 equivalents, particularly preferably 1 to 2 equivalents. If the amount of compound (C) used is too small, the yield of polyester resin with the desired structural moiety introduced tends to be low, and if the amount used is too large, carbon dioxide gas will be generated due to the decomposition of compound (C). However, it tends to become trapped in the system, causing gelation, and is not economical.

[Basic compound (D) having Group 15 element]
The method for producing a polyester resin of the present invention is carried out in the presence of the compound (C) represented by the above general formula (1) and a basic compound (D) having a Group 15 element as a catalyst. By reacting the polyester resin (A) with the active hydrogen group-containing compound (B) in the presence of the basic compound (D) containing a Group 15 element together with the above compound (C), the desired reaction can be efficiently achieved. A polyester resin into which structural moieties have been introduced can be obtained.

In the present invention, "in the presence of a catalyst" means that the catalyst only needs to be present in at least some stages of the reaction process, and does not need to be always present in all stages of the reaction process. In the method for producing a polyester resin of the present invention, if a catalyst is added to the reaction system, the requirement "in the presence of a catalyst" is satisfied. For example, even if some change occurs in the catalyst during the reaction process after the catalyst is added to the reaction system at any stage, the requirement of "in the presence of a catalyst" is satisfied.

Examples of the Group 15 element constituting the basic compound (D) having a Group 15 element include nitrogen, phosphorus, arsenic, antimony, and bismuth, with nitrogen and phosphorus being preferred, and nitrogen and phosphorus being particularly preferred. is preferred. The above basic compound (D) having a Group 15 element may be used alone or in combination of two or more.
Furthermore, as the basic compound having a nitrogen element, an amine compound is preferable because it has high catalytic activity and can yield a polyester resin into which a desired structural moiety is introduced in a high yield.

Examples of the amine compounds include aliphatic amine compounds, aromatic amine compounds, and heterocyclic amine compounds.

Examples of the aliphatic amine compounds include:
Aliphatic primary amine compounds such as methylamine, ethylamine, ethylenediamine, hexamethylenediamine;
Aliphatic secondary amine compounds such as dimethylamine and diethylamine;
Trimethylamine, triethylamine, triethanolamine, N,N-diisopropylethylamine, tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'',N''- Pentamethyldimethylenetriamine, N,N,N',N'',N''-Pentamethyldiethylenetriamine, Bis(2-dimethylaminoethyl)ether, N,N,N',N'',N''- Aliphatic tertiary amine compounds such as pentamethyldipropylenetriamine, N,N-dimethylaminoethanol, N,N-dimethylaminoethoxyethanol;
etc.

Examples of the aromatic amine compounds include aniline, toluidine, 1,8-bis(dimethylamino)naphthalene, and the like.

Examples of the above-mentioned heterocyclic amine compounds include pyrrolidine, piperazine, N'-methylpiperazine, N-(2-dimethylaminoethyl)-N'-methylpiperazine, morpholine, N-ethylmorpholine, N-(N' , N',-2-dimethylaminoethyl) morpholine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, pyrrole, imidazole, pyridine, oxazole, thiazole, N,N-dimethyl-4-aminopyridine, etc. can be mentioned.

Among the above-mentioned amine compounds, aliphatic amine compounds and heterocyclic amine compounds are preferred, and more preferably is an aliphatic amine compound, especially a tertiary amine compound, and particularly preferably triethylamine.

The amount of the basic compound (D) containing a Group 15 element is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyester resin (A). Parts by weight, particularly preferably 0.5 to 5 parts by weight. If the amount of the basic compound (D) containing a Group 15 element is too small, it will tend to be difficult to obtain the effect of further increasing the yield of the polyester resin into which the desired structural moiety has been introduced. Even if the amount of the basic compound (D) containing the element is too large, there is a tendency that no further improvement in yield is observed, which is not economical.

<Method for producing polyester resin with desired structural site introduced>
The production method of the present invention involves combining a polyester resin (A) and an active hydrogen group-containing compound in the presence of a compound (C) represented by the above general formula (1) and a basic compound (D) having a Group 15 element. (B).
Hereinafter, the method for producing the polyester resin of the present invention will be described in detail.

The reaction conditions in the method for producing a polyester resin of the present invention are not particularly limited, and the reaction conditions can be changed as appropriate during the reaction process.

The form of the reaction vessel used in the above reaction is not particularly limited. In addition, raw materials used in the reaction [polyester resin (A), active hydrogen group-containing compound (B), compound (C)], catalyst [basic compound having a Group 15 element (D), magnesium compound (E ), alkali metal compound (F)], etc., into the reaction vessel is not particularly limited. Examples include a method of introducing the catalyst etc. into the reaction vessel in stages, a method of introducing some or all of the raw materials, catalyst etc. into the reaction vessel continuously. Furthermore, these methods may be combined.

The reaction temperature between the polyester resin (A) and the active hydrogen group-containing compound (B) is not particularly limited, but the reaction can be carried out at a relatively low temperature, usually 0 to 150°C, preferably 20 to 120°C. , particularly preferably from 40 to 100°C, particularly preferably from 50 to 90°C. If the reaction temperature is too low, the reaction efficiency tends to decrease, and if the reaction temperature is too high, the main chain of the polyester resin tends to be cut, resulting in a decrease in molecular weight.
Note that if the reaction is carried out without the presence of compound (C), the reaction will be required at a higher temperature than the above temperature range, and the main chain of the polyester resin will be cleaved, making it impossible to obtain a polyester resin with the desired structure. It tends to get harder.

Further, the reaction time is not particularly limited, but is usually 0.5 to 72 hours, preferably 2 to 48 hours, and more preferably 5 to 24 hours. If the reaction time is too short, the reaction tends not to proceed sufficiently, and if the reaction time is too long, the yield tends not to improve, which is not economical.

Furthermore, in the reaction between the polyester resin (A) and the active hydrogen group-containing compound (B), the atmosphere and pressure during the reaction are not particularly limited.

In the method for producing a polyester resin of the present invention, a polyester resin (A) and an active hydrogen group-containing compound (B) are reacted in the presence of a compound (C) and a basic compound (D) having a Group 15 element. In this process, it is preferable to coexist at least one of a magnesium compound (E) and an alkali metal compound (F) as a catalyst, and it is particularly preferable to coexist both. When the reaction is carried out in the presence of these catalysts, an unsaturated group-containing polyester resin can be obtained in higher yield.

[Magnesium compound (E)]
Examples of the magnesium compound (E) include magnesium oxides, hydroxide salts, carbonates, hydrogen carbonates, silicates, sulfates, ammonium sulfate salts, nitrates, phosphates, hydrogen phosphates, Salts with inorganic acids such as ammonium phosphates, borates, halides, perhalates, and hydrohalides; salts with organic acids such as carboxylates, percarboxylate, and sulfonates. Examples include complex salts such as acetylacetone salt, hexafluoroacetylacetone salt, porphyrin salt, phthalocyanine salt, and cyclopentadiene salt. These magnesium salts may be either hydrates or anhydrides. Among these, oxides, hydroxide salts, carbonates, sulfates, ammonium sulfate salts, nitrates, hydrohalides, carboxylates, and complex salts of magnesium are preferred.

More specifically, the preferred magnesium compound (E) includes, for example, magnesium oxide, magnesium hydroxide, magnesium carbonate hydroxide (also known as basic magnesium carbonate), magnesium sulfate, ammonium magnesium sulfate, magnesium nitrate, magnesium chloride, Examples include magnesium oxide, magnesium acetate, magnesium benzoate, magnesium (meth)acrylate, and magnesium bis(2,4-pentanedionato). Among these, magnesium hydroxide and bis(2,4-pentanedionato)magnesium are preferred, and magnesium hydroxide is particularly preferred.

Although commercially available magnesium compounds (E) can be used, those produced by known methods may also be used. Further, the magnesium compound (E) can be used alone or in combination of two or more types.

The amount of the magnesium compound (E) used is preferably 0.001 to 1000 mol%, more preferably 0.005 to 100 mol%, based on the active hydrogen group possessed by the active hydrogen group-containing compound (B). , particularly preferably 0.01 to 5 mol%. If the amount of magnesium compound (E) used is too small, it tends to be difficult to obtain the effect of further increasing the yield of the polyester resin into which the desired structural moieties have been introduced. Even if it is too high, there is a tendency that no further improvement in yield is observed and it is not economical.

[Alkali metal compound (F)]
Examples of the alkali metal compound (F) include hydride salts, oxides, hydroxide salts, carbonates, hydrogen carbonates, sulfates, nitrates, phosphates, borates, and halogen acids of alkali metals. salts, salts with inorganic acids such as perhalates, hydrohalides, thiocyanates; salts with organic acids such as alkoxide salts, carboxylates, sulfonates; amide salts, sulfonamide salts, etc. Salts with organic bases; complex salts such as acetylacetone salts, hexafluoroacetylacetone salts, porphyrin salts, phthalocyanine salts, and cyclopentadiene salts; and the like. These alkali metal salts may be either hydrated or anhydrous. Further, these may be used alone or in combination of two or more. Among these, oxides, hydroxide salts, carbonates, hydrogen carbonates, hydrohalides, carboxylates, amide salts, and complex salts of alkali metals are preferred.

Further, as the alkali metal constituting the alkali metal compound (F), for example, lithium, sodium, potassium, rubidium, and cesium are preferable, and a polyester-based material having high catalytic activity and a desired structural moiety introduced in high yield. Lithium is more preferred since it can yield resin.

Specifically, the above-mentioned lithium compounds include, for example, lithium oxide, lithium hydroxide, lithium carbonate, lithium fluoride, lithium chloride, lithium bromide, lithium acetate, lithium benzoate, lithium (meth)acrylate, and lithium amide. , lithium trifluimide, lithium acetylacetone, and the like. Among them, lithium hydroxide is preferred.

As the alkali metal compound (F), commercially available ones can be used, but those produced by known methods can also be used. Moreover, the alkali metal compound (F) may be used alone or in combination of two or more kinds.

The amount of the alkali metal compound (F) used is preferably 0.001 to 1000 mol%, preferably 0.005 to 100 mol%, based on the active hydrogen group possessed by the active hydrogen group-containing compound (B). Particularly preferred is 0.01 to 5 mol%. If the amount of the alkali metal compound (F) used is too small, it tends to be difficult to obtain the effect of further increasing the yield of the polyester resin into which the desired structural moieties have been introduced. If the amount is too large, no further improvement in yield tends to be observed and it is not economical.

Furthermore, in the method for producing a polyester resin of the present invention, a solvent can also be used as another optional component. As the above-mentioned solvent, the same solvents as those listed in the production of the polyester resin (A) can be used. One type of solvent may be used alone, or a mixed solvent of two or more types may be used. The amount of solvent used is also not particularly limited and can be selected as appropriate. The method of introducing the solvent into the reaction vessel is not particularly limited, but all the solvents may be introduced at once, some or all of the solvents may be introduced in stages, or some or all of the solvents may be introduced in stages. Alternatively, all solvents may be introduced continuously. Alternatively, an introduction method that combines these methods may be used.

Thus, by the production method of the present invention, a polyester resin into which desired structural sites are introduced can be obtained.

[Polyester resin with desired structural parts introduced]
The polyester resin obtained by the production method of the present invention has a structural moiety represented by the following general formula (2) in the side chain of the polyester resin.

The above X portion represents a single bond or a connected chain. That is, the above X portion may be directly bonded to the main chain of the polyester resin, or may be bonded to the main chain of the polyester resin as a connecting chain consisting of carbon atoms, hydrogen atoms, heteroatoms, etc. .
The above R is an organic group in which the second carbon atom adjacent to the second oxygen atom of the side chain ester does not have a hydroxyl group.
Further, when the polyester resin obtained by the production method of the present invention is used for a primer layer (primer composition), from the viewpoint of water resistance, it is preferable that the organic group does not have a hydroxyl group derived from an epoxy group.

The acid value of the polyester resin into which a desired structural moiety is introduced, which is obtained by the production method of the present invention, is preferably 0 to 100 mgKOH/g, particularly 2 to 70 mgKOH/g, particularly 5 to 50 mgKOH/g, and more preferably 5 to 50 mgKOH/g. is preferably 10 to 40 mgKOH/g.

Further, the introduction rate of the active hydrogen group-containing compound (B) to the polyester resin into which the desired structural site has been introduced is usually 0.1% or more, preferably 2% or more, and particularly preferably 10% or more. Note that the upper limit of the above introduction rate is usually 100%.

Hereinafter, the characteristics of the unsaturated group-containing polyester resin, which is one of the preferable embodiments of the polyester resin obtained by the production method of the present invention, will be explained.

[Unsaturated group-containing polyester resin]
The above unsaturated group-containing polyester resin can be obtained by using a hydroxyl group-containing (meth)acrylate as the active hydrogen group-containing compound (B). A composition containing this unsaturated group-containing polyester resin can be suitably used as a primer layer (primer composition) for adhering a substrate and a coating layer.

A crosslinked structure is formed by reacting the unsaturated group-containing polyester resin with a crosslinking agent described below. By forming this crosslinked structure, the molecular mobility of the polyester structure portion of the unsaturated group-containing polyester resin is restricted. On the other hand, the unsaturated groups present in the side chains of the unsaturated group-containing polyester resin have a relatively high degree of steric and spatial freedom even in the unsaturated group-containing polyester resin in which a crosslinked structure has been formed. be. Therefore, for example, when the above unsaturated group-containing polyester resin is used in a primer composition for forming a primer layer provided between a base film and a coating layer, the unsaturated groups of the polyester resin of the present invention are reactive. It segregates on the surface of the primer layer as a sexual group.

Therefore, when a prism layer formed by curing a solvent-free active energy ray-curable resin composition is laminated as a coating layer on the primer layer, in the curing process of the prism layer by irradiation with active energy rays, The unsaturated groups in the primer layer segregated on the surface and the active species derived from the carbon-carbon double bonds in the prism layer react and bond between the layers, increasing their adhesion to each other.

The content of unsaturated groups in the unsaturated group-containing polyester resin is usually 0.005 to 5 mmol/g, preferably 0.01 to 4 mmol/g, particularly 0.03 to 2 mmol/g, and even 0.05 to 1 mmol/g is preferable. If this content is too low, there is a tendency that sufficient adhesion cannot be obtained due to insufficient reaction points with the prism layer, and if this content is too high, the crosslinking reaction will proceed within the unsaturated group-containing polyester resin. The coating film tends to become hard and the adhesion tends to decrease.

The content of unsaturated groups in the unsaturated group-containing polyester resin can be determined by the following formula (I).
Content of unsaturated groups (mmol/g) = (P1 _m × P1 _n )/(P1 _mw × S1) (I)
In formula (I), P1 _m is the weight (mg) of the hydroxyl group-containing (meth)acrylate, P1 _n is the number of unsaturated groups per molecule of the hydroxyl group-containing (meth)acrylate, and P1 _mw is the molecular weight of the hydroxyl group-containing (meth)acrylate. (g/mol), S1 is the solid weight (g) of the unsaturated group-containing polyester resin.
Further, the content of unsaturated groups in the unsaturated group-containing polyester resin can also be measured by NMR.

The glass transition temperature (Tg) of the unsaturated group-containing polyester resin is preferably -5 to 70°C, more preferably 0 to 60°C, particularly preferably 5 to 50°C, and even more preferably 15 to 40°C. If the glass transition temperature of the unsaturated group-containing polyester resin is too low, the solubility or dispersibility in aqueous solvents and blocking resistance tend to decrease, while if the glass transition temperature is too high, the adhesion tends to decrease. be.

The weight average molecular weight of the unsaturated group-containing polyester resin is preferably 3,000 to 200,000, particularly 5,000 to 50,000, particularly 8,000 to 40,000, and even more preferably 10,000 to 30,000. If the weight average molecular weight is too low, adhesion and heat-and-moisture resistance tend to decrease, while if the weight average molecular weight is too high, adhesion and solubility or dispersibility in aqueous solvents tend to decrease.

The above-mentioned unsaturated group-containing polyester resin can be suitably used as a primer composition as described above. The primer composition will be explained below.

[Primer composition]
The primer composition contains an unsaturated group-containing polyester resin, and preferably further contains a crosslinking agent.

The above-mentioned crosslinking agent may be one that causes a crosslinking reaction with the carboxy group in the unsaturated group-containing polyester resin, such as isocyanate compounds, oxazoline compounds, epoxy compounds, carbodiimide compounds, amine compounds, metals, etc. Examples thereof include aziridine-based compounds, aziridine-based compounds, hydrazine-based compounds, hydrazide-based compounds, and melamine-based compounds.

The above-mentioned isocyanate compound may be any compound containing at least two isocyanate groups as a functional group in its molecule, such as aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, etc. aliphatic polyisocyanates such as isophorone diisocyanate, alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, and their biuret and isocyanurate forms, as well as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor. Examples include adducts that are reactants with low-molecular active hydrogen-containing compounds such as oils.

Examples of commercially available isocyanate compounds include "Aquanate 110" and "Aquanate 210" manufactured by Nippon Polyurethane Co., Ltd., "Elastron BN-27" and "Elastron BN-77" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Examples include "Meikanate TP-10" and "SU-268A" manufactured by Meisei Chemical Co., Ltd., and "Trixene aqua BI200" and "Trixene aqua BI220" manufactured by Baxenden Chemical Limited.

Among these, aliphatic isocyanate compounds or alicyclic isocyanate compounds are preferred in order to avoid yellowing due to ultraviolet rays.
In addition, from the viewpoint of stability, functional group block type products are preferred, and "SU-268A", "Trixene aqua BI220", etc. are suitable.

Examples of the above-mentioned oxazoline compounds include addition-polymerizable 2-oxazolines (for example, 2-isopropenyl-2-oxazolines) having a substituent having an unsaturated carbon-carbon bond at the 2-position carbon position, and other unsaturated oxazolines. Examples include copolymers with monomers, and commercially available products include "Epocross WS-500", "Epocross WS-700", "Epocross K-2010E", and "Epocross K-2020E" manufactured by Nippon Shokubai Co., Ltd. ”, “Epocross K-2030E”, etc.).

Examples of the above epoxy compounds include bisphenol A/epichlorohydrin type epoxy resin, sorbitol polyglycidyl ether (for example, "Denacol EX-611", "Denacol EX-612", and "Denacol EX-614" manufactured by Nagase ChemteX). ", "Denacol EX-614B", "Denacol EX-622", etc.), polyglycerol polyglycidyl ether (for example, "Denacol EX-512", "Denacol EX-521", etc. manufactured by Nagase ChemteX), pentaerythritol Polyglycidyl ethers (for example, "Denacol EX-411" manufactured by Nagase ChemteX, etc.), diglycerol polyglycidyl ethers (for example, "Denacol EX-421", etc. manufactured by Nagase ChemteX), glycerol polyglycidyl ethers (for example, , "Denacol EX-313", "Denacol EX-314", etc. manufactured by Nagase ChemteX), trimethylolpropane polyglycidyl ether (such as "Denacol EX-321" manufactured by Nagase ChemteX), resorcinol diglycidyl Ether (for example, "Denacol EX-201" manufactured by Nagase ChemteX, etc.), neopentyl glycol diglycidyl ether (for example, "Denacol EX-211", etc. manufactured by Nagase ChemteX), 1,6-hexanediol di Glycidyl ether (for example, "Denacol EX-212" manufactured by Nagase ChemteX, etc.), hydrogenated bisphenol A diglycidyl ether (for example, "Denacol EX-252" manufactured by Nagase ChemteX, etc.), ethylene glycol di- Glycidyl ether (for example, "Denacol EX-810", "Denacol EX-811", etc. manufactured by Nagase ChemteX), diethylene glycol diglycidyl ether (for example, "Denacol EX-850", "Denacol EX", manufactured by Nagase ChemteX), -851", etc.), polyethylene glycol diglycidyl ether (for example, "Denacol EX-821", "Denacol EX-830", "Denacol EX-832", "Denacol EX-841", "Denacol EX-832", "Denacol EX-841", manufactured by Nagase ChemteX), EX-861", etc.), propylene glycol diglycidyl ether (for example, "Denacol EX-911" manufactured by Nagase ChemteX, etc.), polypropylene glycol diglycidyl ether (for example, "Denacol EX-941" manufactured by Nagase ChemteX) , "Denacol EX-920", "Denacol EX-931", etc.). Among these, aqueous types are preferred, and in particular, bifunctional and linear structures such as ethylene glycol diglycidyl ether and diethylene glycol diglycidyl ether are preferred from the viewpoint of adhesion between the coating layer and the primer layer.

The above-mentioned carbodiimide compound may contain at least two or more carbodiimide groups or cyanamide groups having a tautomeric relationship as a functional group in the molecule, such as "Carbodilite V" manufactured by Nisshinbo Chemical Co. -02'', ``Carbodilite V-02-L2'', ``Carbodilite SV-02'', ``Carbodilite V-04'', ``Carbodilite V-10'', ``Carbodilite E-03A'', ``Carbodilite E-02'', ``Carbodilite E-04'', etc. Among them, from the viewpoint of adhesion between the coating layer and the primer layer, those having aromatic groups such as xylylene skeleton, tolylene skeleton, diphenylmethane skeleton, and tetramethylxylylene skeleton are preferable, and in particular, "Carbodilite V-04", " Carbodilite E-04'' and the like are suitable.

Examples of the above amine compounds include hexamethylene diamine, triethanolamine, and the like.

Examples of the metal compounds include metal alkoxides such as tetraethyl titanate, tetraethyl zirconate, and aluminum isopropionate, and aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Examples include acetylacetone and acetoacetate of polyvalent metals, metal chelate compounds of ethylenediaminetetraacetic acid coordination compounds, acetic acid-ammonium complex salts, ammonium-carbonate complex salts, and the like.

The above-mentioned aziridine compound may be any compound containing at least two aziridine groups, and examples thereof include "Chemitite PZ-33" and "Chemitite DZ-22E" manufactured by Nippon Shokubai Co., Ltd.

The above-mentioned hydrazine compound may contain at least two or more hydrazine groups, and examples thereof include hydrazine monohydrochloride, hydrazine dihydrochloride, hydrazine monohydrobromide, hydrazine carbonate, and the like.

Examples of the hydrazide compounds include adipic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide, isophthalic acid dihydrazide, and salicylic acid hydrazide.

Examples of the above-mentioned melamine-based compounds include hexamethoxymethylol melamine, "Nicalac MW-30M", "Nicalac MW-30", "Nicalac MW-22", "Nicalac MS-11", and "Nicalac MS-11" manufactured by Sanwa Chemical Co., Ltd. Methylated melamine resins such as Nikalak MS-011, Nikalak MX-730, Nikalak MX-750, Nikalak MX-706, Nikalak MX-035, Nikalak MX-45, Nikalak MX Examples include mixed etherified melamine resins such as "-410".

As the crosslinking agent, only one type selected from these may be used, or two or more types may be used in combination.

Among these, the crosslinking agent is preferably at least one compound selected from the group consisting of isocyanate compounds and carbodiimide compounds, with isocyanate compounds being particularly preferred, from the viewpoint of adhesion between the coating layer and the primer layer. .

In particular, it is preferable for the primer layer to be thin in terms of cost and transparency, but if the thickness is thin, adhesion tends to decrease, so when forming a nano-order thin film by in-line coating, etc. The use of agents is particularly effective.

The content of the above crosslinking agent can be selected as appropriate depending on the amount of functional groups contained in the unsaturated group-containing polyester resin, the molecular weight of the unsaturated group-containing polyester resin, and the purpose of use. The weight ratio of the crosslinking agent (weight of unsaturated group-containing polyester resin/weight of crosslinking agent) is preferably from 99/1 to 30/70, particularly from 95/5 to 40/60, particularly from 90/10 to 50/50, more preferably 80/20 to 60/40.
If the content of the crosslinking agent is too high or too low, the adhesiveness and heat-and-moisture resistance tend to decrease due to insufficient crosslinking.

Further, the content of unsaturated groups in the unsaturated group-containing polyester resin with respect to the primer composition is preferably 0.003 to 4 mmol/g, particularly preferably 0.005 to 1 mmol/g, and more preferably 0.01 to 1 mmol/g. 0.5 mmol/g is preferred.
If this content is too low, sufficient adhesion may not be obtained due to a lack of reactive points with the coating layer, while if this content is too high, the crosslinking reaction progresses within the primer composition, causing the paint film to deteriorate. It tends to become hard and reduce adhesion.

The content of unsaturated groups in the unsaturated group-containing polyester resin in the primer composition can be determined by the following formula (II).
Content of unsaturated groups (mmol/g) = (P2 _m × P2 _n )/(P2 _mw × S2) (II)
In formula (II), P2 _m is the weight (mg) of the hydroxyl group-containing (meth)acrylate, P2 _n is the number of unsaturated groups per molecule of the hydroxyl group-containing (meth)acrylate, and P2 _mw is the molecular weight of the hydroxyl group-containing (meth)acrylate. (g/mol), S2 is the total solid weight (g) of the primer composition.

In addition to the above-mentioned components, the primer composition may optionally include a curing catalyst, antioxidants such as hindered phenol, heat stabilizers, glass fibers, inorganic/organic fillers, colorants, flame retardants, Softeners, dispersants, wetting agents, emulsifiers, gelling agents, antifoaming agents, other thermoplastic resins, and the like can be added to the extent that they do not impair the effectiveness of the primer composition. Further, these may be used alone or in combination of two or more.

The method for producing the primer composition is not particularly limited, and for example, each component may be appropriately mixed using a stirring device.

The primer composition or the unsaturated group-containing polyester resin is usually used as an aqueous liquid dissolved or dispersed in an aqueous solvent.

[Aqueous liquid]
The above aqueous liquid can be prepared by appropriately mixing the unsaturated group-containing polyester resin or the primer composition and the aqueous solvent. For example, (1) after preparing the primer composition, mixing the aqueous solvent. (2) A method in which the unsaturated group-containing polyester resin and the crosslinking agent are each made into an aqueous liquid with an aqueous solvent, and these are mixed to form an aqueous liquid. (3) An unsaturated group-containing polyester resin Examples include a method in which either the resin or the crosslinking agent is made into an aqueous liquid using an aqueous solvent, and the remaining components are further mixed to form an aqueous liquid, but method (2) above is preferred in terms of ease of preparation.

Examples of the aqueous solvent include water or a mixture of water and a suitable hydrophilic organic solvent. Examples of the hydrophilic organic solvent include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, and isopropyl alcohol; and glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monotert-butyl ether. etc., which can be mixed with water. When a hydrophilic organic solvent is used, the proportion of the aqueous liquid to the entire solvent is appropriately set. For example, the proportion of the hydrophilic organic solvent to the entire aqueous liquid can be set within a range of 30% by weight or less, but is not limited thereto. Moreover, one type selected from these aqueous solvents may be used, or two or more types may be used in combination.

When preparing the above aqueous liquid, it is preferable to mix a neutralizing agent in order to uniformly dissolve or disperse it in the aqueous medium. Any material may be used as long as it can neutralize the carboxyl group of the resin (including the crosslinking agent if the crosslinking agent contains a carboxyl group).

Specific examples of the neutralizing agent include metal hydroxides such as lithium hydroxide, potassium hydroxide, and sodium hydroxide; ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, iminobispropylamine, - Ethoxypropylamine, 3-diethylaminopropylamine, diethanolamine, triethanolamine, N,N-diethylethanolamine, N,N-dimethylethanolamine, aminoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, etc. Examples include organic amines; and ammonia. One type selected from these neutralizing agents may be used, or two or more types may be used in combination.

Among these neutralizing agents, those having a boiling point of 150° C. or lower, particularly 100° C. or lower are preferred from the viewpoint of being easily volatilized by drying and ensuring the water resistance of the obtained film. In particular, ammonia and triethylamine are preferred, with ammonia being particularly preferred, from the viewpoints of high versatility, low boiling point, and easy volatilization during drying.

Moreover, a surfactant such as an anionic surfactant or a nonionic surfactant can be added to this aqueous liquid as required. By blending a surfactant, it is possible to improve the wettability of an aqueous liquid to a base film such as a polyester film when the aqueous liquid is applied to the base film.

Appropriate surfactants can be used, such as polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl sulfate, alkyl sulfonate, Examples include alkyl sulfosuccinates, dodecylbenzenesulfonates, and the like.
One type selected from these surfactants may be used, or two or more types may be used in combination.
In addition, from the viewpoint of the adhesion between the coating layer and the primer layer and the water resistance of the primer layer, it is preferable not to add a surfactant.

Further, the aqueous liquid may further contain, for example, an antistatic agent, a filler, an ultraviolet absorber, a lubricant, a coloring agent, etc., if necessary. Further, these may be used alone or in combination of two or more.

The solid content concentration of the aqueous liquid is appropriately adjusted so as to ensure good dispersibility of the unsaturated group-containing polyester resin, and is preferably, for example, 5 to 30% by weight. In addition, during coating, it is diluted as appropriate to obtain a desired film thickness, for example, the solid content concentration is adjusted to 1 to 15% by weight.

Hereinafter, a base film with a primer layer obtained using the above aqueous liquid will be explained.

[Base film with primer layer]
By applying the above aqueous liquid to a base film and heating and drying it, a film (primer layer) in which the unsaturated group-containing polyester resin in the primer composition is crosslinked with a crosslinking agent is formed, and the primer layer A base film can be obtained.

Examples of the base film include polyester resins such as polyethylene naphthalate, polyethylene-2,6-naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate/isophthalate copolymer; polyethylene, polypropylene, polymethylpentene, etc. polyolefin resins; polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyethylene fluoride; polyamides such as nylon 6 and nylon 6,6; polyvinyl chloride, polyvinyl chloride/vinyl acetate copolymers, and ethylene- Vinyl polymers such as vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, and vinylon; Cellulose resins such as cellulose triacetate and cellophane; polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, Examples include a monolayer or a multilayer body selected from acrylic resins such as polybutyl acrylate; films or sheets made of synthetic resins such as polystyrene, polycarbonate, polyarylate, and polyimide.
Among these, polyester films are preferably used in terms of transparency, chemical resistance, heat resistance, mechanical strength, cost, and the like.
The above-mentioned polyester film may be either unstretched or stretched, but it is preferable to use a stretched film, and particularly preferably to use a biaxially stretched film.

As a method for applying the aqueous liquid, a commonly known method can be used, such as a method of applying the aqueous liquid to one or both sides of the base film by kiss coating, reverse coating, gravure coating, die coating, or the like.

Further, the thickness of the primer layer after heat drying (after crosslinking) is preferably 0.01 to 2 μm, more preferably 0.02 to 0.5 μm, particularly 0.03 to 0.3 μm, particularly The thickness is preferably 0.05 to 0.15 μm. If the thickness is too thin, adhesion tends to decrease, and if the thickness is too thick, optical properties such as transparency and haze, and blocking resistance tend to decrease.

A laminated film or a prism sheet can be obtained by further providing a coating layer on the primer layer of the base film with a primer layer and using the coating layer as a hard coat layer or a prism layer.

Examples of materials forming the coating layer include acrylic resins, epoxy resins, urethane resins, and active energy ray-curable resin compositions, which are commonly used as coating materials. A synthetic resin composition is preferred.

Specifically, an active energy ray-curable resin composition is coated on the primer layer of the base film with a primer layer and cured by irradiation with active energy rays, thereby forming the primer of the base film with a primer layer. A laminated film having a hard coat layer formed by curing the active energy ray-curable resin composition on the layer can be obtained.

The thickness of the hard coat layer is usually 0.5 to 15 μm, preferably 1 to 10 μm, and particularly preferably 2 to 7 μm.

Furthermore, a prism sheet can be obtained by forming a prism layer on the primer layer of a base film with a primer layer.

The prism layer is preferably a prism layer formed by curing an active energy ray-curable resin composition, and particularly preferably a prism layer formed by curing a solvent-free active energy ray-curable resin composition. be.

When the prism layer is a prism layer formed by curing an active energy ray curable resin composition, the method for forming the prism layer includes, for example, introducing the active energy ray curable resin composition into a prism shape, The active energy ray-curable resin composition is sandwiched between the primer layer and the primer layer side of a base film with a primer layer (especially, a polyester film), and then active energy rays are irradiated to harden the resin composition and form a prism shape. An example of this method is to remove the active energy ray-curable resin composition to form a prism layer on the base film.

The method for applying the active energy ray-curable resin composition is not particularly limited, and examples include spray, shower, dipping, roll, spin, curtain, flow, slit, die, gravure, comma, dispenser, Wet coating methods such as screen printing, inkjet printing, etc. may be mentioned.

Examples of active energy rays that can be used include far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X-rays and gamma rays, as well as electron beams, proton beams, and neutron beams. Curing by ultraviolet irradiation is advantageous from the viewpoint of equipment availability, cost, etc.

As a method of curing by ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc. that emit light in the wavelength range of 150 to 450 nm are used. It is sufficient to irradiate about 30 to 3000 mJ/cm ² .
After irradiation with ultraviolet rays, heating may be performed as necessary to ensure complete curing.

The thickness of the prism layer is preferably 5 to 50 μm, particularly 10 to 45 μm, more preferably 15 to 40 μm, and particularly preferably 20 to 35 μm.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, in the following, "parts" and "%" are based on weight.
Further, the method for measuring each physical property value regarding the polyester resin is as follows.

(1) Method for measuring glass transition temperature Glass transition temperature was determined by measuring using a differential scanning calorimeter. The measurement conditions were a measurement temperature range of -90 to 100°C and a temperature increase rate of 10°C/min.

(2) Method for measuring hydroxyl value The hydroxyl value (mgKOH/g) is determined by dissolving 1 g of polyester resin in 30 g of a mixed solvent of toluene/pyridine = 5/5 (weight ratio) and performing neutralization titration based on JIS K0070. Ta.

(3) Method for measuring acid value Acid value (mgKOH/g) is determined by dissolving 1 g of polyester resin in 30 g of a mixed solvent of methyl ethyl ketone/water = 10/1 (weight ratio), and stirring at room temperature (23°C) for 1 hour. After that, it was determined by neutralization titration based on JIS K0070.
In the present invention, the acid value of the polyester resin is determined by the content of carboxy groups in the resin.

(4) Peak top molecular weight and weight average molecular weight The peak top molecular weight and weight average molecular weight were measured using a column (TSKgel SuperMultipore HZ-M (exclusion limit molecular weight: 2× 10 ⁶ , number of theoretical plates: 16,000 plates/piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 4 μm) were used in series to determine the molecular weight of standard polystyrene.

(5) Method for determining content of unsaturated groups The content of unsaturated groups (mmol/g) was determined by the following formula (Ia).
Content of unsaturated groups (mmol/g) = P1' _m / (P1' _mw × S1')... (Ia)
In formula (Ia), P1' _m is the weight (mg) of PEGMA, P1' _mw is the average molecular weight (g/mol) of PEGMA (calculated from the hydroxyl value), and S1' is the obtained unsaturated group-containing polyester resin. solid content weight (g). In addition, the above-mentioned PEGMA means "polyethylene glycol monoacrylate used in the reaction".

Prior to Examples, a polyester resin (A) having a carboxyl group in its side chain was produced.

[Manufacture example 1]
[Production of polyester resin (A-1) having a carboxyl group in the side chain]
288.4 parts (1.736 mol) of isophthalic acid (IPA) as a polyhydric carboxylic acid component and 156 parts of diethylene glycol (DEG) as a polyol component were placed in a reaction vessel equipped with a thermometer, stirrer, rectification column, and nitrogen inlet tube. 6 parts (1.476 mol), 63.3 parts (0.608 mol) of neopentyl glycol (NPG), and 0.3 parts of tetrabutyl titanate as a catalyst were charged, and the temperature was raised over 150 minutes until the internal temperature reached 270°C. Then, an esterification reaction was carried out at 270°C for 2.5 hours.
Next, the internal temperature was lowered to 170°C, and 91.7 parts (0.347 mol) of 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride was added. An addition reaction was carried out at 170° C. for 1 hour to obtain a polyester resin (A-1) having a carboxyl group in the side chain (hydroxyl value: 2.2 mgKOH/g).
The physical property values of the polyester resin (A-1) measured according to the above measurement method are shown in Table 1 below.

[Manufacture example 2]
[Production of polyester resin (A-2) having a carboxyl group in the side chain]
In a reaction vessel equipped with a thermometer, a stirrer, a rectification column, and a nitrogen inlet tube, 320.1 parts (1.927 mol) of isophthalic acid (IPA) as a polyhydric carboxylic acid component and 173.1 parts (1.927 mol) of diethylene glycol (DEG) as a polyol component were added. 8 parts (1.638 mol), 50.2 parts (0.0.482 mol) of neopentyl glycol (NPG), and 0.3 parts of tetrabutyl titanate as a catalyst were added, and the mixture was heated for 150 minutes until the internal temperature reached 270°C. The temperature was raised and the esterification reaction was carried out at 270°C for 2.5 hours.
Next, 532.2 parts of methyl ethyl ketone was added while lowering the internal temperature to 80°C, and when the resin was completely dissolved, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1, Adding 56.0 parts (0.212 mol) of 2-dicarboxylic anhydride and 2.7 parts of triethylamine as a catalyst, an addition reaction was carried out at 80°C for 3 hours to obtain a polyester resin having a carboxyl group in the side chain (A-2 ) (hydroxyl value: 0.2 mgKOH/g) was obtained.
The physical property values of the polyester resin (A-2) measured according to the above measurement method are shown in Table 1 below.

An unsaturated group-containing polyester resin was produced using the polyester resins (A-1) and (A-2) obtained above.

[Example 1]
[Production of unsaturated group-containing polyester resin 1]
After dissolving 100 parts of the polyester resin (A-1) obtained above in 100 parts of methyl ethyl ketone, 39.7 parts of polyethylene glycol monoacrylate 1 (PEGMA1, average molecular weight calculated from hydroxyl value: 540), dicarbonate di- 17.5 parts of t-butyl (1.09 equivalents relative to the hydroxyl group of PEGMA1), 11.4 parts of methyl ethyl ketone, 0.005 part of hydroxide value magnesium (II) as a catalyst (0.1 mol% relative to the hydroxyl group of PEGMA1) ), 0.012 parts of lithium hydroxide (0.4 mol % based on the hydroxyl group of PEGMA1), and 1.4 parts of triethylamine were charged into a reactor, and the reaction was carried out at 80° C. for 3 hours. When the molecular weight of the obtained reaction mixture was measured using the above-mentioned GPC, as shown in Table 2 below, the molecular weight was increased compared to the polyester resin (A-1), indicating that the unsaturated group introduction reaction was confirmed to be in progress. Moreover, the acid value of the unsaturated group-containing polyester resin 1 was 35.6 mgKOH/g, and the unsaturated group content was 0.53 mmol/g.

[Example 2]
[Production of unsaturated group-containing polyester resin 2]
200 parts of the polyester resin (A-2) solution with a solid content of 50% obtained above (solid content 100 parts), polyethylene glycol monoacrylate 2 (PEGMA2, average molecular weight calculated from hydroxyl value: 163.1)8. 69 parts, 11.63 parts of di-t-butyl dicarbonate (1.0 equivalent to the hydroxyl group of PEGMA2), 54 parts of methyl ethyl ketone, 0.06 parts of bis(2,4-pentanedionato)magnesium(II) as a catalyst (0.5 mol% based on the hydroxyl group of PEGMA2), 0.01 part of lithium hydroxide (0.5 mol% based on the hydroxyl group of PEGMA2), and 1.1 parts of triethylamine were charged into a reactor and heated at 70°C for 18 hours. The reaction was carried out. Next, 2.3 parts of di-t-butyl dicarbonate (0.2 equivalent to the hydroxyl group of PEGMA) was added, and the reaction was further carried out at 70°C for 18 hours. When the molecular weight of the obtained reaction mixture was measured using the above-mentioned GPC, as shown in Table 2 below, the molecular weight was increased compared to the polyester resin (A-2), indicating that the unsaturated group introduction reaction was confirmed to be in progress. Further, the acid value of the unsaturated group-containing polyester resin 2 was 22.3 mgKOH/g, and the unsaturated group content was 0.49 mmol/g.

From the results in Table 2, it was confirmed that since Examples 1 and 2 were produced according to the production method of the present invention, the unsaturated group introduction reaction progressed and the molecular weight increased.

[Preparation of unsaturated group-containing polyester resin di-aqueous dispersion]
37.5 parts of the unsaturated group-containing polyester resin 2 solution with a solid content of 40% obtained above, 62.05 parts of deionized water, and 0.45 parts of 25% aqueous ammonia were charged into a reactor and stirred at room temperature. While dispersing the mixture in water, an aqueous liquid (aqueous dispersion) of unsaturated group-containing polyester resin 2 having a solid content concentration of 15% was prepared.

[Preparation of primer composition]
The unsaturated group-containing polyester resin 2 aqueous liquid (aqueous dispersion) obtained above, the blocked isocyanate crosslinking agent "Trixene Aqua BI220" (manufactured by Lanxess Chemicals Limited), and the curing catalyst "Elastron CAT-21" (Daiichi (manufactured by Kogyo Seiyaku Co., Ltd.) were mixed at a solid content weight ratio of unsaturated group-containing polyester resin 2:crosslinking agent:curing catalyst=70:30:1 as shown in Table 3 below, and the mixture was heated at room temperature. A primer composition was prepared by stirring for 1 hour.
The obtained primer composition was evaluated as follows.

[Adhesion evaluation]
The primer composition obtained above was diluted with deionized water to a solid content of 3% to prepare a coating liquid of the primer composition. The prepared coating liquid was coated on PET film "Lumirror T60" (manufactured by Toray Industries, Ltd., thickness 100 μm) using bar coater No. 6 and dried at 150° C. for 3 minutes to form a primer layer.

<Adhesion evaluation 1>
(Initial adhesion)
Next, a solvent-free ultraviolet curable resin composition "Sunrad A" (manufactured by Sanyo Chemical Industries, Ltd.) for forming a prism layer was applied onto the primer layer using an applicator, and then at a height of 13 cm from the applied surface. The ultraviolet curable resin composition was cured by irradiating it with ultraviolet rays at 400 mJ/cm ² using a high-pressure mercury lamp with an irradiation intensity of 80 W/cm set in the same position as above, to form a resin layer with a thickness of 25 μm.

100 crosscuts of 1 mm ² were placed in the ultraviolet curable resin layer thus formed, and Sellotape (registered trademark) manufactured by Nichiban Co., Ltd. was pasted on top of the crosscuts, and the tape was rubbed with a plastic eraser to ensure sufficient adhesion. Thereafter, it was rapidly peeled off in a 90° direction, and the degree of peeling of the ultraviolet curable resin layer, that is, the number of remaining ultraviolet curable resin layers per 100 crosscuts, was counted, and the adhesion was evaluated based on the following criteria.

[Evaluation criteria]
(Remaining number/measured number)
◎: 95/100 or more ○: 80/100 or more, 94/100 or less △: 51/100 or more, 79/100 or less ×: 50/100 or less

(Moisture heat resistant adhesion)
The laminated film having the cured resin layer of Sunrad A obtained in the same manner as above was left undisturbed for 96 hours in an environment of 85°C and 85% RH, and then left undisturbed for 1 hour in an environment of 23°C and 50% RH. The adhesion was evaluated using the same method as above.

<Adhesion evaluation 2>
(Initial adhesion)
Evaluation was carried out in the same manner as Initial Adhesion Evaluation 1 except that the solvent-free ultraviolet curable resin composition for forming the prism layer was changed to "BTW-607-1" (manufactured by Dongguan Shell New Materials Co., Ltd.) The adhesion was evaluated using the same method as above.

(Moisture heat resistant adhesion)
A laminated film having a cured resin layer of BTW-607-1 obtained in the same manner as above was left to stand in an environment of 85°C and 85% RH for 96 hours, and then left to stand in an environment of 23°C and 50% RH. After standing for 1 hour, adhesion was evaluated using the same method as above.
These evaluation results are also shown in Table 3 below.

From the results in Table 3 above, it was confirmed that the polyester resin having an unsaturated group produced by the production method of the present invention has excellent performance as a primer.

According to the production method of the present invention, a desired structural site can be introduced into the side chain of a polyester resin.

Claims (10)

A polyester resin (A) having a carboxyl group in the side chain and a compound (B) containing an active hydrogen group are combined with a compound (C) represented by the following general formula (1) and a basic compound having a Group 15 element ( D) A method for producing a polyester resin, wherein the active hydrogen group contained in the active hydrogen group-containing compound (B) is at least one selected from the group consisting of an amino group, a mercapto group, and a hydroxyl group. A method for producing a polyester resin, characterized in that the basic compound (D) having a Group 15 element is an amine compound.

The polyester resin (A) and the active hydrogen group-containing compound (B) are combined in the presence of the compound (C) represented by the general formula (1) and the basic compound (D) containing a Group 15 element. 2. The method for producing a polyester resin according to claim 1, further comprising coexisting one or more magnesium compounds (E) during the reaction. The polyester resin (A) and the active hydrogen group-containing compound (B) are combined in the presence of the compound (C) represented by the general formula (1) and the basic compound (D) containing a Group 15 element. 3. The method for producing a polyester resin according to claim 1, further comprising coexisting one or more alkali metal compounds (F) during the reaction. The method for producing a polyester resin according to any one of claims 1 to 3, wherein the active hydrogen group-containing compound (B) is an active hydrogen group-containing (meth)acrylate. The method for producing a polyester resin according to any one of claims 1 to 4, wherein the compound (C) represented by the general formula (1) is di-t-butyl dicarbonate. 4. The method for producing a polyester resin according to claim 3, wherein the alkali metal constituting the alkali metal compound (F) is lithium. Any one of claims 1 to 6, characterized in that 0.05 to 20 parts by weight of the basic compound (D) having the Group 15 element is coexisting with 100 parts by weight of the polyester resin (A). A method for producing a polyester resin according to item 1. It is characterized in that the compound (C) represented by the above general formula (1) is allowed to coexist in the presence of 0.8 to 5 equivalents to the active hydrogen group possessed by the above active hydrogen group-containing compound (B). A method for producing a polyester resin according to any one of claims 1 to 7. The method for producing a polyester resin according to claim 2, characterized in that the magnesium compound (E) is present in an amount of 0.001 to 1000 mol% with respect to the active hydrogen group possessed by the active hydrogen group-containing compound (B). . 7. The polyester resin according to claim 3 or 6 , wherein the alkali metal compound (F) is present in an amount of 0.001 to 1000 mol% with respect to the active hydrogen group possessed by the active hydrogen group-containing compound (B). Production method.