WO2019123731A1 - Siloxane-type curable resin composition and hard coating liquid - Google Patents

Abstract

Provided is a curable resin composition that can rapidly cure in the air and that is useful for a hard coating material having an excellent scratch resistance, transparency, etc. The siloxane-type curable resin composition comprises the partial hydrolysis-condensation product of the following component (A) and component (B) and is characterized in that the partial hydrolysis-condensation product has an epoxy equivalent weight (g/eq) of 200 to 4,000: component (A): isocyanurate ring structure-bearing alkoxysilane or partial hydrolysis-condensation product thereof; and component (B): epoxy group- or oxetane group-bearing alkoxysilane or partial hydrolysis-condensation product thereof.

Description

Siloxane-based curable resin composition and hard coating liquid

The present invention relates to a siloxane-based curable resin composition useful as a hard coating liquid excellent in abrasion resistance, transparency, low curling property, and the like. This composition is applicable to various hard coating materials, such as electronic parts, such as a display and a case, an interior of a car, a household appliance member, and a construction member, for example.

In recent years, from the viewpoint of weight reduction and design, a member in which the surface of a resin base material is protected with a hard coat material having high scratch resistance has been used as an alternative to metal and glass. In the hard coating material, a heart coating solution is usually applied to a resin substrate to be protected, and an acrylic composition is often used as such a hard coating solution.
Acrylic compositions are generally formed by radical reaction by irradiation of active energy rays such as ultraviolet rays and electron beams, so that they can be cured in a short time at a low temperature, and toughness can be maintained by compounded resin compositions. It is widely used in adhesives and the like. However, when the curing by the radical polymerization reaction is carried out in the air, it is affected by the inhibition of oxygen, and therefore sufficient scratch resistance can not be ensured only by increasing the amount of the radical polymerization initiator. Therefore, equipment of an inert gas atmosphere such as nitrogen is required, but such special equipment also has problems such as an increase in process cost.

On the other hand, as a general curing method that can be cured in the air, a method in which a metal acylate or a curing agent is mixed with an epoxy resin or a siloxane-based composition having a hydrolyzable silyl group and cured at heating or room temperature However, when the resin base requires curing under low temperature conditions, there is a problem that it takes a long time to obtain a sufficient cured state.

On the other hand, as an atmospheric curing method by photocuring that can be cured in a short time, cationic curing materials using an epoxy resin, an alkoxysilane condensate having an epoxy group alone, or a combination thereof are reported (Patent Documents 1 to 3). In any case, many alkoxysilane condensates used are silsesquioxanes using highly cationic curable alicyclic epoxy groups. Therefore, hydrolysis condensation under a basic catalyst rather than under an acidic catalyst is applied as a condensation catalyst in order to prevent the ring opening of the epoxy group. In general, siloxane condensates synthesized under a basic catalyst consist of cage type, random type and ladder type, and most of them are cage type rigid structures, and furthermore, the crosslinked structure by alicyclic epoxy group is also rigid. Because of this, the resulting film has a problem that it is fragile while it is high in hardness.

WO2014 / 204010 JP, 2015-212353, A JP, 2015-053397, A

The present invention has been made to solve the above-mentioned problems, and as a hard coating material which can be cured in the atmosphere in a short time and is excellent in scratch resistance and transparency, low curlability, flexibility and the like. It is an object of the present invention to provide a useful curable resin composition and its hard coating solution.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research in order to achieve the said objective, the present inventors discover that the said subject can be solved by the siloxane type curable resin composition of the formulation containing a specific alkoxysilane, and came to this invention.

（式中、Ｒ^１は炭素数１～１５の有機基を示し、Ｒ^２は水素原子又は炭素数１～５のアルキル基を示し、Ｒ^３は炭素数１～６の有機基を示し、ａは０～２の数を示し、Ｘは独立に水素原子、炭素数１～１５の有機基又は式（ii）で表されるシリルアルキル基を示す。）

（式中、Ｒ^１～Ｒ^３及びａは、上記式（i）と同意である。）
（Ｂ）成分；下記式（iii）で表されるエポキシ基又はオキセタン基を有するアルコキシシラン又はその部分加水分解縮合物、
　　　Ｒ^４ _ｂＲ^５ _ｃＳｉ（ＯＲ^６）_{４－ｂ－ｃ}　　　　（iii）
（式中、Ｒ^４、Ｒ^５はいずれも直接Ｓｉに結合し、Ｒ^４はエポキシ基又はオキセタン基を含む炭素数１～１５の有機基を示し、Ｒ^５はエポキシ基及びオキセタン基をいずれも含まない炭素数１～１０の有機基を示し、Ｒ^６は水素原子または炭素数１～５のアルキル基を示し、ｂ、ｃはそれぞれ０＜ｂ≦１、０≦ｃ≦２の数を示し、ｂ＋ｃは０＜ｂ＋ｃ≦２の数を示す。）。 That is, this invention is a partial hydrolysis-condensation product which is the partial hydrolysis-condensation product of the following (A) component and (B) component, Comprising: Epoxy equivalent (g / eq) is 200-4000, as the 1st aspect It is a siloxane-based curable resin composition characterized by including:
Component (A): an alkoxysilane having an isocyanurate ring structure represented by the following general formula (i) or a partial hydrolytic condensate thereof,

(Wherein, R ¹ represents an organic group having 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ represents an organic group having 1 to 6 carbon atoms, a Represents a number of 0 to 2, and X independently represents a hydrogen atom, an organic group having 1 to 15 carbon atoms, or a silylalkyl group represented by the formula (ii).

(Wherein, R ¹ to R ³ and a have the same meaning as in the above formula (i))
Component (B): an alkoxysilane having an epoxy group or an oxetane group represented by the following formula (iii) or a partial hydrolysis condensate thereof:
R ⁴ _b R ⁵ _c Si (OR ⁶ ) _4-b-c (iii)
(Wherein, R ⁴ and R ⁵ are both directly bonded to Si, R ⁴ is an organic group having 1 to 15 carbon atoms including an epoxy group or an oxetane group, and R ⁵ is both an epoxy group and an oxetane group R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and b and c each represent a number of 0 <b ≦ 1 and 0 ≦ c ≦ 2. , B + c represents a number of 0 <b + c ≦ 2).

The siloxane-based curable resin composition preferably has a ratio of component (A) to component (B) of 0.01 to 7 moles of component (A) per 1 mole of component (B).

In the first aspect of the present invention, the above-mentioned siloxane-based curable resin composition is a hard coating solution containing a curing catalyst as component (C) and an organic solvent as component (D).

In the first aspect of the present invention, a method of forming a hard coating film characterized in that the above-mentioned siloxane-based curable resin composition is applied to an underlayer or a substrate, dried and then cured by active energy ray irradiation or heating. It is. Furthermore, this may be heat-treated.

A second aspect of the present invention is a partially hydrolyzed condensate of the above components (A) and (B), which has an epoxy equivalent (g / eq) of 200 to 4000, A siloxane-based curable resin composition comprising: a cationic photopolymerization initiator as the component C '); and a surface conditioner as the component (E):
(C ') component; photo cationic polymerization initiator (E) component; a surface conditioner comprising a fluorine compound, a dimethylsiloxane compound, or a modified product or derivative thereof.

The siloxane-based curable resin composition preferably has a ratio of component (A) to component (B) of 0.01 to 7 moles of component (A) per 1 mole of component (B).
The component (E) is preferably a surface conditioner having a reactive group that forms a covalent bond with the partial hydrolytic condensate of the components (A) and (B).

In the second aspect of the present invention, the siloxane-based curable resin composition contains an organic solvent as the component (D).

In a second aspect of the present invention, a method of forming a hard coating film is characterized in that the above-mentioned siloxane-based curable resin composition is applied to an underlayer or a substrate and dried, and then cured by active energy ray irradiation. . Furthermore, it is a cured film obtained by curing the above-mentioned siloxane-based curable resin composition.

According to a third aspect of the present invention, there is provided a partially hydrolyzed condensate of the components (A) and (B), wherein the partially hydrolyzed condensate has an epoxy equivalent of 200 to 4000 (g / eq). A laminate comprising a base resin layer and a hard resin layer formed from a hard coating solution containing a siloxane-based curable resin, a curing catalyst as component (C), and an organic solvent as component (D). is there.

In the laminate of the present invention, the hard resin layer and the base material may be laminated via a resin layer composed of a single layer or a plurality of layers, and a surface treatment layer may be formed on the base material.

In another aspect of the present invention, a hard coating liquid containing the above-mentioned siloxane-based curable resin composition is applied to a substrate, a resin layer, or a surface-treated substrate, dried and then irradiated with active energy rays or heated. It is a method of producing a hard coating film characterized by curing. By this, a hard siloxane resin layer which consists of a hard coating film can be formed on a substrate layer via a resin layer if needed, and it becomes a layered product by which a hard coating film was formed in the surface.

The siloxane-based curable resin composition of the present invention comprises a partial hydrolytic condensate of the components (A) and (B). This partial hydrolytic condensate has an epoxy equivalent of 200 to 4000 (g / eq). The siloxane-based curable resin composition of the present invention may consist only of the above-mentioned partial hydrolysis condensate, or may contain other components.

The siloxane-based curable resin composition of the present invention is a curing catalyst for the component (C), a cationic photopolymerization initiator for the component (C '), (C) together with the partial hydrolytic condensates of the components (A) and (B). It is preferable to include the organic solvent of the component D) and the surface conditioner of the component (E), and it may further include components other than the components (A) to (E).

The component (A) is an alkoxysilane having an isocyanurate ring structure represented by the above general formula (i) or a partial hydrolysis condensate thereof. The component (A) having an isocyanurate ring structure causes the condensation product or the cured product to have a multi-branched structure, so that it is considered that the bond is extended in three dimensions and the brittleness is improved.
In the general formula (i), R ¹ represents an organic group having 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents an organic group having 1 to 6 carbon atoms. And a represents a number of 0 to 2, and X independently represents a hydrogen atom, an organic group having 1 to 15 carbon atoms, or a silylalkyl group represented by the formula (ii). In the formula (i) and the formula (ii), the common symbols have the same meaning.
When R ¹ , R ² , R ³ and X are organic groups, they are preferably hydrocarbon groups, more preferably alkyl groups, alkenyl groups and cycloalkyl groups. In addition, when carbon number is six or more, it may be an aromatic hydrocarbon group.
As X, preferably at least one is a silylalkyl group represented by formula (ii), and more preferably, two of X are all silylalkyl groups represented by formula (ii). a is preferably 0 or 1.

Here, the above partial hydrolysis condensate is a dimer or more, and means a condensate having an alkoxysilane group or a hydroxyl group, which is partially dimerized and partially hydrolyzed and partially condensed. On the other hand, completely hydrolyzed condensates are distinguished by the fact that the hydroxyl groups are almost consumed by the condensation reaction and the condensation reaction does not proceed any further.

Examples of the alkoxysilane having an isocyanurate ring structure represented by the general formula (i) include 1,3,5-tris (methyldimethoxysilylpropyl) isocyanurate and 1,3,5-tris (methyldiethoxysilyl). Propyl) isocyanurate, 1,3,5-tris (trimethoxysilylpropyl) isocyanurate, 1,3,5-tris (trimethoxysilylethyl) isocyanurate, 1,3- (di-2-propene-1-) Yl) -5- (3-triethoxysilylpropyl) isocyanurate, 1- (2-propen-1-yl) -3,5-bis (3-triethoxysilylpropyl) isocyanurate, 1,3-bis ( 3-Trimethoxysilylpropyl) isocyanurate, 1-glycidylmethyl-3,5-bis (3-trimethoxysilylpropyl) isocyanurate 1, 3-bis (glycidylmethyl) -5- (3-trimethoxysilylpropyl) isocyanurate, 1-glycidylmethyl-3- (2-propen-1-yl) -5- (3-triethoxysilyl) And propyl) isocyanurate, 1,3-dimethyl-5- (3-triethoxysilylpropyl) isocyanurate and the like. Preferably, 1,3,5-tris (trimethoxysilylpropyl) isocyanurate, 1,3,5-tris (methyldiethoxysilylpropyl) isocyanurate, 1,3,5-tris (trimethoxysilylpropyl) isocyanate A nurate, 1,3,5-tris (trimethoxysilylethyl) isocyanurate.

The component (B) is a siloxane resin which is an alkoxysilane having an epoxy group or an oxetane group represented by the above formula (iii) or a partial hydrolysis condensate thereof. It is considered that the scratch resistance and storage stability are improved by the component (B) having an epoxy group or an oxetane group.

In the formula (iii), R ⁴ is an organic group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, which contains an epoxy group or an oxetane group. R ⁵ is an organic group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, which contains neither an epoxy group nor an oxetane group. R ⁶ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 2 carbon atoms. The organic group in R ⁴ and R ⁵ is preferably an alkyl group, and the organic group in R ⁴ is preferably an alkyl group having a glycidyl group, an alicyclic epoxy group and an oxetane group at the end. The calculation of the carbon number of the organic group in R ⁴ does not include the carbon number of the epoxy group or the oxetane group. When it contains the carbon number which an epoxy group or an oxetane group has, 2 to 3 are added to the said carbon number.

In formula (iii), b and c each represent a number (average value) of 0 <b ≦ 1 and 0 ≦ c ≦ 2, and b + c satisfies 0 <b + c ≦ 2. 4-b-c is preferably a number of 2 or 3. b is preferably 0.1 or more.

Examples of the alkoxysilane having an epoxy group or an oxetane group represented by the formula (iii) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 4-glycidoxybutyltrimethoxy, for example. Silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxy (2-ethyl) propyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, 8-glycidoxyoctyl Triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-[(3-ethyloxetane-3-yl] ) Methoxy] propyltrimethoxysilane etc Silane compounds having Jo ether can be exemplified. Preferably, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-[(3-ethyloxetan-3-yl) methoxy] propyltrimethoxysilane is there.

The partial hydrolysis condensate of the alkoxysilane of Formula (iii) is obtained by carrying out the partial hydrolysis of this like the alkoxysilane of Formula (i).

The blending ratio (molar ratio) is preferably 0.01 to 7 moles, and more preferably 0.01 to 1.5 moles, per 1 mole of the component (B).

The partial hydrolysis condensates of the components (A) and (B) are partial hydrolysis condensates of a mixture containing the components (A) and (B). The mixture containing the component (A) and the component (B) can contain other silane compounds or (partial) hydrolysates thereof unless the object of the present invention is inhibited.
As other silane compounds, for example, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane , Octyltriethoxysilane, decyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltriol Methoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrime Xylan, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxy And alkoxysilanes such as propylmethyldimethoxysilane. These organosilanes can be used alone or in combination of two or more.

The partial hydrolysis condensates of the components (A) and (B) are partial hydrolysis condensates of a mixture containing the components (A) and (B). The hydrolysis is preferably performed to such an extent that all of the alkoxy groups are hydrolyzed to become OH groups, but the condensation to form a siloxane bond by condensation of Si—OH groups is in a state of being partially performed. If condensation proceeds too much, it gels and can not be dissolved or dispersed in a solvent. Further, after partially hydrolyzing the components (A) and (B) alone, they may be mixed and further subjected to hydrolysis and condensation.

These hydrolytic condensates are siloxane resins, and the average molecular weight (Mw) thereof is preferably 300 to 60000, more preferably 400 to 30000.

The partial hydrolytic condensates of components (A) and (B) have an epoxy group or an oxetane, and have an epoxy equivalent of 200 to 4000, preferably 200 to 1000, and more preferably 200 to 500. The molecular weight can also be calculated from this epoxy equivalent.
In the present invention, the partial hydrolytic condensate does not contain the catalyst or solvent added during hydrolysis, water which remains unreacted, water produced by condensation, and only the Si-containing compound produced by partial hydrolytic condensation, It is a so-called siloxane resin component.
If the epoxy equivalent (g / eq) is less than the lower limit of the epoxy equivalent, scratch resistance and storage stability will be reduced. When the epoxy equivalent exceeds the upper limit, the resulting film becomes brittle and the toughness decreases. In the resin composition of the present invention, the epoxy equivalent refers to the mass of a siloxane resin having one equivalent of an epoxy group, and does not include the mass of a solvent or the like. In addition, even if it is a case where (B) component does not have an epoxy group but has an oxetane group, since an oxetane equivalent becomes the same value as an epoxy equivalent, it can be understood as an epoxy equivalent.
In addition, you may adjust the epoxy equivalent in a composition by adding an epoxy resin with (B) component. As such an epoxy resin, a general purpose bifunctional epoxy resin such as bisphenol type epoxy resin or a multifunctional epoxy resin such as phenol novolac epoxy resin can be used.

In the hydrolysis method, in order to obtain a linear siloxane structure, the solution may be hydrolyzed with acidic water of pH 1 to 7, preferably pH 2 to 5. For this pH adjustment, an organic acid such as hydrochloric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, methanesulfonic acid, toluenesulfonic acid or the like Inorganic acids can be used. Moreover, you may use the cation exchange resin etc. which have a carboxylic acid group and a sulfonic acid group on the surface. The amount of the acid or acid catalyst used is preferably 0.0001 to 20% by weight with respect to the product (partially hydrolyzed condensate).

The hydrolysis reaction requires the presence of water. The amount of water may be an amount sufficient to hydrolyze (part of) the hydrolyzable group in the above silane compound, and may be 0.5 to 0.5 of the theoretical amount (mol) of the number of hydrolyzable groups. Preferably, the amount corresponds to 2.0 times mol. More preferably, it is 0.7 to 1.5 times mol. Also, if the acid or catalyst is added as an aqueous solution, add that water to the calculation. When the amount of water is small, sufficient hydrolysis does not proceed, and when the amount is large, the remaining water reduces the coating property and the drying efficiency.

The dehydration condensation reaction of the silanol group generated simultaneously with the hydrolysis occurs to form a siloxane resin composition. The temperature at which this condensation is performed is normal temperature or heating at 120 ° C. or less, more preferably 30 ° C. or more and 100 ° C. or less. When the temperature is low, the time for hydrolysis and condensation reaction is long, the productivity is low, and when the temperature is high over the range, there is a possibility of insolubilization.

Various organic solvents may be mixed in order to adjust the reaction rate of the above hydrolysis and condensation and the molecular weight of the resin composition to be produced. For example, alcohols such as methanol, ethanol, butanol, isobutanol, isopropyl alcohol, propanol, t-butanol, sec-butanol, benzyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, Examples of diacetone alcohol and ester include ethyl acetate, methyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, isopropyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, butyl lactate and ethers. Isopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, glycols such as ethylene glycol, diethylene glycol, triethylene glycol Propylene glycol, as glycol ester type, ethylene glycol monoethyl ether acetate, methoxypropyl acetate, butyl carbitol acetate, ethyl carbitol acetate, as glycol ether type, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl diglycol, methyl Triglycol, 1-methoxy-2-propanol, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, diethylene glycol monohexyl ether, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, ethylene glycol dimethyl ether , Diethylene glycol dimethyl ether, ethylene glycol di Chirueteru, diethylene glycol diethyl ether, the aromatic hydrocarbon, benzene, toluene, xylene. These organic solvents can be used alone or in combination of two or more.

The amount of the organic solvent mixed is preferably 10 parts by weight to 2000 parts by weight, based on 100 parts by weight of the total amount of the components to be hydrolyzed. However, when the compounding quantity of (B) component is large, it can also hydrolyze and condense by the non-solvent which does not use an organic solvent.

The resin composition in the first aspect of the present invention may be only the above-mentioned partial hydrolysis condensate, but the partial hydrolysis condensate has an epoxy group or an oxetane group and is also epoxy resins, so It is good to mix | blend as a (C) component the curing catalyst for making it cure | harden.
As the curing catalyst (C), a curing agent (acid generator or base generator) capable of generating an acid or a base by heating or active energy ray irradiation, or a curing accelerator can be applied. Examples of the curing agent that generates an acid or a base include diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, and ammonium salts.
Specific examples of the heat or photoacid generator include San-Aid SI series (manufactured by Sanshin Chemical Co., Ltd.), TA or CPI series (manufactured by San-Apro), Adeka Ark SP Series (manufactured by ADEKA), WPI series (Japanese An example can be manufactured by Mitsuko Junyaku Co.). Specific examples of the photobase generator include WPBG series (manufactured by Wako Pure Chemical Industries, Ltd.), O0395, A2502 (manufactured by Tokyo Kasei Kogyo Co., Ltd.), EIPBG (manufactured by I-Bite KK), and the like.
In the case of curing by active energy rays, a photosensitizer or a photosensitizer such as a radical polymerization initiator which exhibits an effect in combination may be used in combination. As a curing accelerator by heating, amine adducts, hydrazides and imidazoles may be mentioned. Specifically, Amicure PN series (manufactured by Ajinomoto Fine Techno Co., Ltd.), Fujicure-FXR series (manufactured by TOKA), an imidazole compound series (manufactured by Shikoku Kasei Co., Ltd.), and the like can be exemplified.

The addition amount of the component (C) is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the partial hydrolysis condensate of the components (A) and (B).
If it is less than this range, the crosslinking becomes insufficient, the elastic modulus decreases, and the desired surface height can not be obtained. Even if added beyond this range, no further improvement in the reaction rate can be expected.

In the resin composition according to the second aspect of the present invention, the partial hydrolytic condensates of the (A) component and the (B) component have an epoxy group or an oxetane group and are also epoxy resins, so they are cured The photocationic polymerization initiator of the above is blended as the component (C ').
The photo cationic polymerization initiator (C ') is also an acid generator which generates an acid (cation) upon irradiation with active energy rays. Examples include diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, oxonium salts, and ammonium salts.
Accordingly, specifically, the above-mentioned San Aid SI series (manufactured by Sanshin Chemical Co., Ltd.), TA or CPI, IK series (manufactured by San Apro), Adeka Ark SP series (manufactured by ADEKA), WPI series (manufactured by Wako Pure Chemical Industries, Ltd.) ), Irgacure series (manufactured by BASF), etc. correspond to this.
Among them, iodonium salts are preferable when thick films and transparency are required. Specifically, IK-1 (manufactured by San-Apro), WPI 113, WPI 116, WPI 170, WPI 124 (manufactured by Wako Pure Chemical Industries, Ltd.), Irg 250 (manufactured by BASF), and the like can be exemplified.
Furthermore, a photosensitizer or a photosensitizer such as a sensitizer and a radical polymerization initiator which exhibit an effect in combination with the initiator may be used in combination.

The addition amount of the component (C ') is preferably 0.1 to 100 parts by weight of the partial hydrolytic condensate of the components (A) and (B), similarly to the curing catalyst of the component (C). It is in the range of 10 parts by weight, more preferably 1 to 7 parts by weight. If it is less than this range, the crosslinking becomes insufficient, the elastic modulus decreases, and the desired surface height can not be obtained. Even if added beyond this range, no further improvement in the reaction rate can be expected. In addition, in 2nd aspect, when it mix | blends with the surface conditioner (E) component mentioned later, the abrasion resistance can be further improved by setting it as 1 weight part or more of range.

The resin composition in the second aspect of the present invention contains a surface conditioner of component (E). The surface control agent is blended for the purpose of improving the leveling property and scratch resistance at the time of film formation. As the surface conditioner, fluorine compounds, dimethylsiloxane compounds, or modified products or derivatives of these compounds (including oligomers and polymers) are used. Specifically, FZ-2123, 57 ADDITIVE (made by Toray Dow Corning), KP124, KP109, KP110, KP121, KP106, KP112 (made by Shin-Etsu Chemical Co., Ltd.), BYK306, BYK307, BYK307, BYK310, BYK313, BYK333, BYK342. (Manufactured by BYK), R40, R41, R43, R94 (manufactured by DIC), Polyflow 401, Polyflow 402, Polyflow 404 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

Further, as the surface conditioner (E) for maintaining the scratch resistance for a long time, a structure having a reactive group incorporated in the crosslinks of partial hydrolytic condensates of the (A) component and the (B) component is preferable. Examples of reactive groups include hydroxyl groups such as carbinol groups and silanol groups, or epoxy groups and mercapto groups, and fluorine compounds and dimethylsiloxane compounds modified with these reactive groups are more preferable.

Specifically, KF-1001, KF1002, KF2001, KF-105, KF-6000, 6001, 6002, 6003, X-22-167B, KF9701, X22-173, X-22-170, X-22-9002. (Shin-Etsu Chemical Co., Ltd.), L-7604, 8029 ADDITIVE, 8054 ADDITIVE, 8211 ADDITIVE, 8526 ADDITIVE (manufactured by Toray Dow Corning), BYK 370, BYK 375, BYK 377, BYK SILCEAN 3700, BYK SILCEAN 3701, BYK SILCEAN 3720 (manufactured by BYK), and the like.

The amount of component (E) added is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight per 100 parts by weight of the partial hydrolysis condensate of components (A) and (B). It is a range of parts by weight.
If this range is not reached, it is not possible to improve the leveling property and the scratch resistance at the time of film formation. Even if it is added beyond this range, no further improvement can be expected, but there is a possibility that other physical properties may be inhibited.

The siloxane-based curable resin composition of the present invention can be made into a hard coating solution by containing an organic solvent as the component (D). Component (D) is an organic solvent. As an organic solvent, the same thing as the organic solvent mixed at the time of hydrolysis can be illustrated, and it may be the same as or different from the solvent mixed at the time of hydrolysis. The compounding amount of the component (D) is preferably 10 parts by weight to 5000 parts by weight, and more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the partial hydrolysis condensate. In addition, the compounding quantity of (D) component is the quantity also including the quantity of the solvent mixed at the time of hydrolysis.

In forming a hard coating film, it is desirable to apply a hard coating solution containing the above-mentioned components on a substrate or a primer layer, dry it, and then light cure it by ultraviolet irradiation. This curing is caused by polymerization of an epoxy group or an oxetane group, and also contributes to a crosslinking reaction by an addition reaction of an epoxy group or an oxetane group with a silanol group and a condensation of a silanol group. After the photocuring, a heating and curing step may be provided in order to sufficiently advance condensation of silanol groups.

Other components can be blended into the composition of the present invention as required. As other components, epoxy resin, acrylic resin, organic / inorganic filler, plasticizer, flame retardant, heat stabilizer, antioxidant, ultraviolet absorber, ultraviolet shielding agent, lubricant, antistatic agent, mold release agent, foaming For example, other resin components such as other siloxane-based resins, organic acrylates or vinyl compounds can be exemplified for the purpose of promoting the reaction, agents, nucleating agents, colorants, crosslinking agents, dispersing aids, and the like. In the case of blending an acrylic resin or an organic acrylate, it is preferable to use a photo radical polymerization initiator in combination, and it is desirable to blend an acrylic group-containing fluorine compound or a dimethylsiloxane compound or a modified product thereof as a surface control agent.

As a method of forming a hard coating film, there may be mentioned, for example, a flow coating method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method and a dipping method. In addition, coating film thickness is adjusted with solid content concentration in consideration of the formed film thickness after hardening by irradiation of an active energy ray, drying.

After application of the hard coating solution, the solvent is preferably removed by drying or the like. The drying temperature is set to a condition that the base material used is not deformed, and the drying time is preferably 1 hour or less from the viewpoint of productivity.

From the viewpoints of scratch resistance and adhesion, the thickness of the hard coating is 0.5 to 20 μm, preferably 1 to 10 μm.

In the hard coating film forming step, in the case of using a photoactive curing catalyst, it is preferable to irradiate the active energy ray under the conditions of an illuminance of 100 mW / cm ² or more and an integrated light amount of 1000 mJ / cm ² or more. When the irradiation dose is low, crosslinking formation is insufficient and the desired scratch resistance performance can not be obtained.

After curing by irradiation with active energy rays, heat treatment may be performed. The curing temperature is set so as not to deform the base material to be used, to accelerate the hydrolysis and condensation of the siloxane resin, and further to diffuse the generated acid or base to accelerate the curing reaction of the epoxy group or the oxetane group. The temperature condition is 70 to 150 ° C., preferably 80 to 120 ° C.

The laminate as the third aspect of the present invention is obtained by forming a hard siloxane resin layer as a hard coating film on a base material layer, optionally through another resin layer.
The hard coating film is formed from a hard coating liquid containing a siloxane-based curable resin containing the partial hydrolytic condensate of the components (A) and (B), a curing catalyst (C) and an organic solvent (D). .

As the base material, any of thermoplastic resin, curable resin, metal, glass, wood, paper, and stone can be applied. Specifically, as a thermoplastic resin, polyvinyl chloride, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, polymethyl methacryl, polyvinyl alcohol, polyvinylidene chloride, polyethylene terephthalate, polyamide, polyacetal, polyphenylene ether , Polycarbonate, polybutylene terephthalate, polyvinylidene fluoride, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, polyamide imide, polyether imide, polyether ether ketone, polyimide, liquid crystal polymer, polytetrafluoroethylene, cycloolefin copolymer, elastomer Etc. Examples of the curable resin include phenol resin, urea resin, melamine resin, polyester resin, acrylic resin, urethane resin, epoxy resin, imide resin, siloxane resin, fluorine resin and the like. As a metal, steel plates, such as aluminum, magnesium, copper, iron, such alloy steel plates, and various plated steel plates are mentioned. As wood, such as zelkova, hinoki, cedar, red pine, abozilla, rosewood, walnut, teak, mahogany, white oak, iron wood, cherry, beech, maple, rubber wood, chestnut, walnut, leek, tuna, pine, pine, etc. Various wood is mentioned. Examples of paper include wood derived from artificial cellulose fiber, eucalyptus, acacia and the like, non-wood derived from hemp, kozo, bamboo and the like, and a composite of this with inorganic fine particles or a resin Etc. Examples of the glass include various glasses such as float glass, tempered glass, heat resistant glass, fire prevention glass, design glass, color glass, laminated glass, heat ray reflective glass and the like. Examples of the stone include natural stones such as igneous rock, sedimentary rock, metamorphic rock and artificial marble.

A single layer or plural resin layers may be interposed between the hard resin layer and the substrate for the purpose of imparting functionality such as adhesiveness and weather resistance or design property, and this resin layer is a single layer In the case of the above, a curable resin such as a commercially available primer material, an adhesive, or a printing material suitable for the base material in the case of a plurality of layers in the case of a plurality of layers can be used. Examples of the resin include acrylic resin, urethane resin, polyurea resin, epoxy resin, phenol resin, siloxane resin, polyimide resin, and polyamideimide resin. Specific examples of the resin species of the resin layer are given below, but are not particularly limited.

As the acrylic resin, a cured resin obtained by curing an acrylic composition containing a polyfunctional acrylic monomer having a molecular weight of 500 or less is preferable. Examples of polyfunctional acrylic monomers include polyfunctional (meth) acrylates. For example, polyfunctional acrylates having two or three (meth) acrylic groups in the molecule are preferable, and aliphatic acrylates, alicyclic acrylates, epoxy An acrylate etc. are mentioned. Moreover, in the acrylic composition containing a polyfunctional acrylic monomer, it is desirable to contain the compound which has an epoxy group, and it is more preferable that it is epoxy group containing polyfunctional acrylic monomers, such as an epoxy acrylate.

Specific examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, and tetraethylene. Glycol dimethacrylate, dicyclopentanyldimethylol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol epoxy acrylate, trimethylolpropane epoxy acrylate, isocyanate and hydroxyl group The urethane acrylate etc. which were made to react the acrylate which it has are mentioned. These (meth) acrylates may be used alone or in combination of two or more.

When curing the above acrylic composition, it is preferable to add a photopolymerization initiator as a polymerization initiator, and the addition amount thereof is 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the resin composition. It is preferable that it is a range. If it is less than this range, the crosslinking becomes insufficient, the elastic modulus decreases, and the desired surface height can not be obtained. On the contrary, if the content is beyond this range, further improvement of the reaction rate can not be expected.

Examples of the urethane resin include cured resins of aliphatic or aromatic polyester polyol compounds and di, tri or polyisocyanate compounds or melamine resins.

Examples of the polyol include polyester polyols obtained by polycondensation of polybasic acid and polyhydric alcohol, polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone, γ-valerolactone, ethylene oxide, propylene oxide And an alkylene oxide such as butylene oxide, a polymer of a cyclic ether such as tetrahydrofuran or an alkyl-substituted tetrahydrofuran, or a polyether polyol which is a copolymer of two or more of these.

Examples of polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, Hexamethylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, lysine diisocyanate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane Triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexame Triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, dicyclopentadiene diisocyanate, norbornene diisocyanate.

The urethane resin may have a reactive group in addition to the above-mentioned reactive group, and examples thereof include an amino group, a (meth) acrylate group, a vinyl group, a mercapto group and an epoxy group.

Examples of polyurea resins include cured resins of polyamine and polyisocyanate. Examples of polyamines include aliphatic amines, aromatic amines, modified amines, which have at least two amino groups and may be primary amines, secondary amines, and tertiary amines. Specifically, 1,2-diaminopropane, 1,5-diamino-2-methylpentane, 1,3-diaminopentane, 1,2-diaminocyclohexane, 1,6-diaminohexane, 1,11-diaminoundecane 1,12-diaminododecane, 3- (cyclohexylamino) propylamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, isophorone diamine, 4,4'-diaminodicyclohexylmethane, 3,3 '-Dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-[1,4-butanediylbis- (oxy) bis] -1-propanamine, menthane diamine, diethylenetriamine, dipropylenetriamine, bis (hexamethylene) Triamine, diethylene tetraamine, triethylene ter Laamine, tetraethylene pentaamine, diethylenetriamine, triethylenetetramine, dipropylenediamine, diethylaminopropylamine, N-aminoethylpiperazine, mensenediamine, isofluorodiamine, m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone Etc. Examples of the polyisocyanate include the same as those described for the urethane resin.

Examples of the epoxy resin include curable resins obtained by curing an epoxy resin having at least two epoxy groups with an isocyanate or melamine resin, and known epoxy group-containing resins such as aliphatic epoxy, aromatic epoxy, modified epoxy and the like It can be used. Specifically, bisphenol epoxy resin, novolac epoxy resin, aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, glycidyl ester epoxy resin and the like can be mentioned. Examples of bisphenol-type epoxy resins include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AD-type epoxy resins, bisphenol S-type epoxy resins, etc., and brominated products and water additives thereof. Examples of novolac epoxy resins include phenol novolac epoxy resins and cresol novolac epoxy resins. Examples of the aromatic epoxy resin include trisphenol methane triglycidyl ether and the like. As the modified epoxy resin, an epoxy ester resin in which a drying oil fatty acid is reacted with a part of the epoxy group of the epoxy group-containing resin, and a polymerizable non-polymerizable resin containing acrylic acid or methacrylic acid in the epoxy group of various epoxy group-containing resins. Epoxy acrylate resin in which a saturated monomer component is reacted, urethane-modified epoxy group-containing resin in which a polyisocyanate compound and a polyol compound are reacted with an epoxy group-containing resin having a hydroxyl group, polyoxyalkylene compound is reacted with an epoxy group-containing resin having a hydroxyl group The polyoxyalkylene modified epoxy group containing resin etc. can be mentioned.

As a phenol resin, although a novolak type resin and a resol type are mentioned, a resol type is preferable, and using together with an epoxy resin is preferable.

The siloxane resin is a curable resin such as a ladder type, random type, cage type, ladder type or the like in which one or more siloxane bonds not included in the claims of the present invention are bonded, and alkoxy group containing siloxane, silanol group containing Siloxane, (meth) acrylic group-containing siloxane, epoxy group-containing siloxane, mercapto group-containing siloxane, amino group-containing siloxane, styryl group-containing siloxane, isocyanate group-containing siloxane, ureido group-containing siloxane, vinyl group-containing siloxane, sulfide group-containing siloxane, etc. Can be mentioned. These reactive functional groups may be used alone or in combination of two or more.

As the polyimide resin, a resin derived from an acid anhydride and an aromatic diamine, a resin derived from an acid anhydride and an aliphatic diamine, or two or more of these may be used in combination, and when there are a plurality of resin layers In order to prevent the appearance of the base layer or the base material from being damaged, a transparent polyimide resin is preferable. Pyromellitic dianhydride (PMDA), naphthalene-2,3,6,7-tetracarboxylic dianhydride (NTCDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) Cyclohexanetetracarboxylic acid dianhydride, phenylenebis (trimellitic acid monoester anhydride), 4,4'-oxydiphthalic acid dianhydride, benzophenone-3,4,3,4 ', 4'-tetracarboxylic acid dianhydride Diphenyl sulfone-3,4,3 ', 4'-tetracarboxylic acid dianhydride 2,3,6,7-naphthalenetetracarboxylic acid dianhydride 4,4'-(2,2'-hexafluoro acid) It is isopropylidene) diphthalic dianhydride etc. On the other hand, as diamines, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylether, 1,3-bis (4-aminophenoxy) benzene, 4,4'-diamino Diphenylsulfone, 2,2-bis (4-aminobenzyloxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4'-diaminobenzanilide, 9,9-bis (4-amino) Phenyl) fluorene etc. are mentioned.

In the laminate of the present invention, the resin composition used for the resin layer may use a photopolymerization initiator, a photoacid generator, and a photobase generator in combination in the case of photocuring in order to accelerate the curing. In the case of heat curing, it is preferable to use a thermal polymerization initiator, a thermal acid generator, an amine-based curing agent, a caprolactone-based curing agent, and the like in combination. The compounding amount of these curing accelerators is preferably 0.1 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition.

The resin composition used for the resin layer is preferably dissolved in a solvent and applied as a solution to a base material or the like to form a layer, and then cured.
Examples of the solvent include organic solvents for the purpose of adjusting the solid content concentration, improving the dispersion stability, improving the coatability, and improving the adhesion to the substrate. For example, alcohols such as methanol, ethanol, butanol, isobutanol, isopropyl alcohol, propanol, t-butanol, sec-butanol, benzyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, Examples of diacetone alcohol and ester include ethyl acetate, methyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, isopropyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, butyl lactate and ethers. Isopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, glycols such as ethylene glycol, diethylene glycol, triethylene glycol Propylene glycol, as glycol ester type, ethylene glycol monoethyl ether acetate, methoxypropyl acetate, butyl carbitol acetate, ethyl carbitol acetate, as glycol ether type, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl diglycol, methyl Triglycol, 1-methoxy-2-propanol, propylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, diethylene glycol monohexyl ether, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, ethylene glycol dimethyl ether , Diethylene glycol dimethyl ether, ethylene glycol di Chirueteru, diethylene glycol diethyl ether, the bicarbonate-based, benzene, toluene, xylene, n-hexane, cyclohexane, heptane, other N- methyl-2-pyrrolidone, N, N- dimethylformamide, etc. γ- butyrolactone. These organic solvents can be used alone or in combination of two or more.

The method of forming the resin layer on the substrate can be formed by applying a solution of various resins and drying, and then either heating or irradiation with active energy rays. As curing conditions, it is preferable that crosslinking is formed so as not to cause white turbidity or elution in the hard coating film forming step to be applied later, and it is preferable that the crosslinking not be completely formed.

As a method of forming a resin layer, for example, a flow coating method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, a spin coating method, a flow coating method, a curtain coating method and a dipping method can be mentioned. In addition, a coating film thickness is adjusted with solid content concentration in consideration of the formation film thickness after drying and hardening.

The resin layer may be mixed with a thermoplastic resin, rubber particles, and the like for the purpose of improving flexibility, adhesion, and the like. The compounding amount is preferably in a range that does not impair the curability of the curable resin, and it is desirable that the thermoplastic resin is 0 to 50 parts by weight with respect to 100 parts by weight of the curable resin.

In the laminate of the present invention, the substrate may be surface-treated to form a surface-treated layer. The surface treatment of the substrate is performed for the purpose of imparting adhesiveness by a hard resin layer or a resin layer and a chemical bonding, or an anchor effect due to electrostatic bonding or unevenness, and general anchor treatment and coupling Agent treatment, ultraviolet irradiation treatment, plasma treatment, corona discharge treatment, blast treatment, brush treatment, polishing treatment, etching treatment, chemical conversion treatment, anodization and the like.

When the base material is a resin, the resin base material may be provided with various wiring such as a thin film of an inorganic material that imparts metallic luster, an electronic circuit, etc., as necessary.

The laminate of the present invention has a hard coating film composed of a hard siloxane resin layer on the surface, is excellent in scratch resistance and transparency, and can be formed by atmospheric curing in a short time, so it is applied to various applications. it can. For example, displays such as touch panels, conductive films, antireflective films, reflective films, diffusion films, shatterproof films, protective films, front plates, housings, buttons, sensors, electronic device members, windows, instrument panels, Exterior parts, partition windows, windshields, head lamps, condensers, insulation films, heat ray shielding films, vehicle members such as decorative films and transfer films, furniture doors and surfaces, floor coverings, doors, window frames, windows, walls , Door knobs, roofs, entrance floors, tiles, bridges, tarpaulins, bottom film, light control films, etc. construction and civil engineering members. Optical components such as lenses, polarizers, wavelength conversion elements, and sensors, buttons and surface members of home appliances, energy-related members such as solar cells, wind power generation, fuel cells, and piezoelectric films. Semiconductor materials such as buffer coats, nonconductive films, cover films, mold release films, resists, cards, inkjet paper, thermal paper, marking films, design films, signs, advertising materials, decorative materials, sign signs, supplies for printers It can be applied to recording and graphic members such as copier rolls and heat sealers, kitchen counters, sinks, vanities, kitchen and sanitary members such as tub walls and ceilings, and various hard coating materials used indoors and out.

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.

Synthesis example 1
In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 1.2 g (1.9 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 3- Add 26.0 g (0.1 mol) of glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403), stir, add 6.4 g of a 0.05% aqueous hydrochloric acid solution to the dropping funnel (water content: hydrolysis) 1 mole of the sex group was added and added with stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, followed by cooling, and 11 g of propylene glycol monomethyl ether (PGME) was added to obtain a solution (a siloxane resin solution A1) of a target partially hydrolyzed condensate. . The epoxy equivalent of the obtained partial hydrolytic condensate was 220.

Synthesis example 2
16.5 g (0.027 mol) of KBM 9659, 1.0 g (0.004 mol) of KBM-403 and 5.9 g of PGME are added to a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, and the mixture is stirred and dropped. Then, 4.7 g of a 0.05% aqueous hydrochloric acid solution was added thereto, and the mixture was added with stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, followed by cooling to obtain a target siloxane condensate (siloxane resin solution A2). The epoxy equivalent of the obtained reactant was 3890.

Synthesis example 3
Add 21.7 g (0.035 mol) of KBM 9659 and 2.5 g (0.1 mol) of KBM-403 into a reaction vessel equipped with a stirrer, dropping funnel, and thermometer, and stir, and add 0.05% hydrochloric acid to the dropping funnel. 11.6 g of an aqueous solution was charged and added with stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, followed by cooling, and 17.6 g of PGME was added to obtain a target siloxane condensate (siloxane resin solution A3). The epoxy equivalent of the obtained reactant was 422, and the molecular weight was 43,600.

Synthesis example 4
30.0 g (0.12 mol) of 3-methacryloxypropyltrimethoxysilane (XIAMETER OFS 6030: manufactured by Toray Dow Corning) in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 0.05% in the dropping funnel 9.3 g of a hydrochloric acid aqueous solution was charged and added while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, and then cooled and 5.8 g of PGME was added to obtain a target siloxane condensate (siloxane resin solution A4, molecular weight 1000).

Examples 1 to 4 and Comparative Example 1
The siloxane resin solutions A1 to A4 obtained in the above synthesis example, the polymerization initiator and the solvent were blended in proportions (parts by weight) shown in Table 1 to obtain siloxane-based curable resin compositions (hard coating liquids) H1 to H5. .
Here, CPI-100 (San Apro) used as a curing catalyst is a photoacid generator, WPBG-266 (Wako Pure Chemical Industries, Ltd.) is a photo base generator, SI-80 (Sanshin Chemical Industries) is a cationic polymerization initiator, Irg 184 (BASF) is a radical photoinitiator and the solvent is PGME.

 

 

Formation and evaluation of hard coating film Siloxane-based curable resin composition (hard coating liquid) H-1, H-2, H-3, H-5 compounded in the ratio of Table 1 above, each with PET substrate The solution was applied by spin coating to a thickness of 100 μm, a length of 10 cm, and a width of 10 cm, dried at 80 ° C. for 6 minutes, and then cooled at room temperature for 5 minutes. Then, it formed into a film by 400 mJ / cm < ² > accumulated exposure amount (365 nm conversion) using a high-pressure mercury lamp of ² kW / cm <2> in oxygen atmosphere.
The siloxane-based curable resin composition (hard coating solution) H-4 of Example 4 was applied to a PET substrate (thickness 100 μm, length 10 cm, width 10 cm) by spin coating, and was applied at 80 ° C. for 6 minutes. After drying, the film was further heated at 100 ° C. for 30 minutes to form a film.

Hard coating evaluation

[Abrasion resistance test 1]
The film test pieces having the hard coating film formed thereon were subjected to 10 reciprocation tests using # 0000 steel wool under a load of 1.0 kg to visually evaluate the number of scratches.
○: 0 or more and less than 5 scratches Δ: 5 or more and 10 or less scratches ×: 10 or more scratches

[Adhesive]
Using a razor blade, cut a film specimen with a hard coating film into the film at intervals of 2 mm in length and 11 rows at a distance of 2 mm to make 100 grids and apply cellophane tape, The presence or absence of peeling when vigorously peeled at an angle of 60 degrees was visually observed, and the number of peeled squares / number of squares was evaluated.
○: 0/100
×: 1/100 to 100/100

  The results are shown in Table 2.

Synthesis example 5
In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 1.2 g (1.9 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 3- Add 26.0 g (0.1 mol) of glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403), stir, add 6.4 g of a 0.05% aqueous hydrochloric acid solution to the dropping funnel (water content: hydrolysis) 1 mole of the sex group was added and added with stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, followed by cooling, and 11 g of propylene glycol monomethyl ether (PGME) was added to obtain a solution (a siloxane resin solution A5) of the objective partially hydrolyzed condensate. . The epoxy equivalent of the obtained partial hydrolytic condensate was 1300.

Synthesis example 6
In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 1.1 g (1.8 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 2- 25.0 g (0.1 mol) of (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-303) is added and stirred, and 5.9 g of 0.05% aqueous hydrochloric acid solution is added to the dropping funnel. Water content: 1 mol of the hydrolyzable group was added and added with stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, followed by cooling, and 11 g of propylene glycol monomethyl ether (PGME) was added to obtain a solution (a siloxane resin solution A6) of the objective partially hydrolyzed condensate. . The epoxy equivalent of the obtained partial hydrolytic condensate was 1000.

Examples 5 to 14 and Comparative Example 2
The siloxane-based curable resin composition was prepared by blending the siloxane resin solutions A5 to A6, the epoxy resin E1, the photocationic polymerization initiator, the surface conditioner, and the solvent obtained in the above synthesis example in the proportions (parts by weight) shown in Table 3. Hard coating solutions) H6 to H16 were obtained.

The symbols in Table 3 are shown.
A5: 3-glycidoxypropyl group-containing siloxane co-condensate A6 obtained in Synthesis Example 5 6: 2- (3,4-epoxycyclohexyl) ethyl group-containing siloxane co-condensate E1 obtained in Synthesis Example 6: Epoxy resin: Celoxide 2021 P (made by Daicel Corporation)
IK-1: diaryliodonium · (Rf) _n PF _6-n salt (manufactured by San Apro)
WPI 170: diaryliodonium · PF ₆ salt (manufactured by Wako Pure Chemical Industries, Ltd.)
WPI116: Diaryl iodonium · SbF ₆ salt 50% propylene carbonate solution (manufactured by Wako Pure Chemical Industries, Ltd.)
CPI 100 P: triarylsulfonium · PF ₆ salt 50% propylene carbonate solution (manufactured by San-Apro Co.)
CPI 101A: triarylsulfonium · SbF ₆ salt 50% propylene carbonate solution (manufactured by San-Apro Co.)
R43: Fluorine-containing group / lipophilic group-containing oligomer (manufactured by DIC)
KF6003: carbinol modified dimethylsiloxane (Shin-Etsu Chemical Co., Ltd.)
BYK 375: Polyether ester modified hydroxyl group-containing polydimethylsiloxane (by BYK)
BYK 377: Polyether modified hydroxyl group-containing polydimethylsiloxane (manufactured by BYK)
PGME: 1-methoxy-2-propanol (manufactured by Kanto Chemical Co., Ltd.)

 

 

Formation of Hard Coating Film The siloxane-based curable resin compositions H6 to H16 obtained in Examples 5 to 14 and Comparative Example 2 were spin-coated on a PET substrate (thickness 100 μm, length 10 cm, width 10 cm) The solution was applied, dried at 80 ° C. for 6 minutes, and cooled at room temperature for 5 minutes. Thereafter, a film test piece with a film thickness of 10 μm was obtained by forming a film with a 400 mJ / cm ² cumulative exposure dose (converted to 365 nm) using a ² kW / cm ² high pressure mercury lamp under an oxygen atmosphere.

Evaluation of hard coating film (film test piece)

Yellowness
The film test pieces were measured using a UV-VIS SPECTROPHOTOMETER UV-3600Plus (manufactured by Shimadzu Corporation) with the PET substrate as a blank.

[Abrasion resistance test 1]
As mentioned above.
[Abrasion resistance test 2]
The film test pieces were subjected to 10 reciprocating tests under a load of 1.5 kg using # 0000 steel wool to visually evaluate the number of flaws.
○: 0 scratch x ×: 1 scratch or more

The results are shown in Table 4.

Next, examples of laminates in which hard coat films are formed on various substrates using the siloxane-based cured claim resin composition of the present invention as a hard coating solution will be described.

Synthesis example 7
In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 2.5 g (4.0 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 3- Add 26.0 g (0.1 mol) of glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403), stir, add 6.7 g of a 0.05% aqueous hydrochloric acid solution to the dropping funnel (water content: hydrolysis) 1 mole of the sex group was added and added with stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, followed by cooling, and 11 g of propylene glycol monomethyl ether (PGME) was added to obtain a solution (a siloxane resin solution A7) of the objective partially hydrolyzed condensate. . The epoxy equivalent of the obtained partial hydrolytic condensate was 220.

Synthesis example 8
In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 2.5 g (4.0 mmol) of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate (Shin-Etsu Chemical Co., Ltd .: KBM 9659) and 2- 26.0 g (0.1 mol) of (3,4-epoxycyclohexyl) ethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-303) is added and stirred, and 6.7 g of a 0.05% aqueous hydrochloric acid solution is added to the dropping funnel. Water content: 1 mol of the hydrolyzable group was added and added with stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, followed by cooling, and 11 g of propylene glycol monomethyl ether (PGME) was added to obtain a solution (a siloxane resin solution A8) of the objective partially hydrolyzed condensate. . The epoxy equivalent of the obtained partial hydrolytic condensate was 250.

Synthesis example 9
30.0 g (0.12 mol) of 3-methacryloxypropyltrimethoxysilane (XIAMETER OFS 6030: manufactured by Toray Dow Corning) in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 0.05% in the dropping funnel 9.3 g of a hydrochloric acid aqueous solution was charged and added while stirring at room temperature. After completion of the dropwise addition, the temperature was raised to 60 ° C. and stirred for 1 hour, and then cooled and 5.8 g of PGME was added to obtain a target siloxane condensate (siloxane resin solution A9).

Adjustment examples 1 to 5
The siloxane resin solutions A7 to A9 obtained in the above synthesis examples, the polymerization initiator and the solvent were blended in proportions (parts by weight) shown in Table 5 to obtain siloxane-based curable resin compositions (hard coating liquids) H17 to H21. .
Here, WPI-116 (manufactured by Wako Pure Chemical Industries, Ltd.) used as a curing catalyst is a photo-acid generator, WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.) is a photo-base generator, SI-80 (manufactured by Sanshin Chemical Industries, Ltd.) ) Is a cationic polymerization initiator, Irg 184 (manufactured by IGM) is a radical photopolymerization initiator, and the solvent is PGME.

 

 

Preparation of resin agent 30 parts by weight of dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .: light acrylate DCP-A), 70 parts by weight of pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co .: UA-306H) 3 parts by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF Japan Ltd .; Irgaqure 819) as a polymerization initiator, and 333 parts by weight of propylene glycol monomethyl ether as a solvent, I got P-1).

Preparation of surface treatment agent Aminosilane coupling agent KBP-40 (manufactured by Shin-Etsu Chemical Co., Ltd .: 30 parts by weight, 35 parts by weight of ethanol and 35 parts by weight of water as a solvent) to obtain a surface treatment composition (S-1) The

Example 15
The hard coating solution H-17 obtained in Preparation Example 1 is applied to a PET substrate (thickness 100 μm, length 10 cm, width 10 cm) by spin coating, dried at 80 ° C. for 6 minutes, and then at room temperature 5 It cooled for a minute. Then, using a ² kW / cm ² high-pressure mercury lamp in an oxygen atmosphere, a film is formed at 1000 mJ / cm ² cumulative exposure dose (365 nm equivalent), and a hard coating (HC) film is formed on the PET substrate surface A coated PET laminate was obtained.

Examples 16, 17 and Comparative Example 3
An HC coated PET laminate was obtained in the same manner as in Example 15 except that the hard coating solution had the composition shown in Table 6, except that a hard coating was formed on the surface of the PET substrate.

Example 18
The hard coating solution H-20 obtained in Preparation Example 4 is applied to a PET substrate (thickness 100 μm, length 10 cm, width 10 cm) by spin coating, dried at 80 ° C. for 6 minutes, and then 100 A film was formed by heating at 30 ° C. for 30 minutes, and a HC coated PET laminate obtained by forming a hard coating film on the surface of the PET substrate was obtained.

Example 19
The coating solution of the resin composition (P-1) is applied to a PC substrate (3 mm thick, 10 cm long, 10 cm wide) by spin coating, dried at 80 ° C. for 6 minutes, and cooled at room temperature for 5 minutes did. Then, the resin layer was formed into a film by 100 mJ / cm < ² > accumulated exposure amount (365 nm conversion) using a ² kW / cm <2> high pressure mercury lamp in oxygen atmosphere. Next, the hard coating solution H-17 obtained in Preparation Example 1 was applied to the resin layer by spin coating, dried at 80 ° C. for 6 minutes, and cooled at room temperature for 5 minutes. After that, using a ² kW / cm ² high-pressure mercury lamp under an oxygen atmosphere, a film is formed at 1000 mJ / cm ² cumulative exposure dose (converted to 365 nm), and a hard coating film is formed on the PC substrate via a resin layer. An HC coated PC laminate was obtained.

Example 20
A solution of a surface treatment agent (S-1) was applied to an aluminum plate by spin coating, the surface of the aluminum plate was treated, and dried at 100 ° C. for 5 minutes. Next, the hard coating solution H-17 obtained in Preparation Example 1 was applied to the resin layer by spin coating, dried at 80 ° C. for 6 minutes, and cooled at room temperature for 5 minutes. Then, an oxygen atmosphere, using a high-pressure mercury lamp of 2 kW / cm ^2, was deposited at 1000 mJ / cm ² cumulative exposure amount (365 nm equivalent), by forming a hard coating film on an aluminum substrate surface-treated HC coating An attached aluminum laminate was obtained.

Example 21
The hard coating solution H-17 obtained in Preparation Example 1 is applied to an aluminum substrate (thickness 500 μm, length 10 cm, width 10 cm) by spin coating, dried at 80 ° C. for 6 minutes, and then at room temperature 5 It cooled for a minute. After that, using a ² kW / cm ² high-pressure mercury lamp in an oxygen atmosphere, a film is formed at 1000 mJ / cm ² cumulative exposure dose (converted to 365 nm), and a hard coating film is formed on the aluminum substrate. I got a body.

Evaluation of hard coating [Abrasion resistance test 1]
The film test pieces having the hard coating film formed thereon were subjected to 10 reciprocation tests using # 0000 steel wool under a load of 1.0 kg to visually evaluate the number of scratches.
○: no scratch ×: one or more scratches

[Adhesive]
Using a razor blade, cut a film specimen with a hard coating film into the film at intervals of 2 mm in length and 11 rows at a distance of 2 mm to make 100 grids and apply cellophane tape, The presence or absence of peeling when vigorously peeled at an angle of 60 degrees was visually observed, and the number of peeled squares / number of squares was evaluated.
○: 0/100
: 1: 1/100 to 50/100
X: 50/100 to 100/100

The results are shown in Table 6.

The siloxane-based curable resin composition of the present invention can be widely used as a paint, a hard coat material, etc. excellent in abrasion resistance and transparency. The composition and the hard coating solution can be widely used as various hard coating materials such as, for example, electronic members such as displays and casings, interiors of automobiles, home electric appliances members, and construction members.
By using the siloxane-based curable resin composition of the present invention as a hard coating solution, atmospheric curing in a short time is possible, and the substrate surface is hard-coated through another resin layer, if necessary. The laminated body formed by forming the hard siloxane resin layer as a film can be provided. This laminate includes, for example, electronic parts such as displays and casings, vehicle members such as interiors and windows, optical members such as furniture and building members lenses, surface members of home appliances, energy related members such as solar cells, buffers The present invention can be applied to various hard coating materials used indoors and outdoors, such as semiconductor members such as coats, graphic members such as recording members and design films, and sanitary members such as kitchen counters and vanities.

Claims (16)

A siloxane-based curable resin comprising: a partial hydrolytic condensate of the following components (A) and (B), wherein the partial hydrolytic condensate has an epoxy equivalent of 200 to 4000 (g / eq): Composition:
Component (A): an alkoxysilane having an isocyanurate ring structure represented by the following general formula (i) or a partial hydrolytic condensate thereof,

(Wherein, R ¹ represents an organic group having 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ represents an organic group having 1 to 6 carbon atoms, a Represents a number of 0 to 2, and X independently represents a hydrogen atom, an organic group having 1 to 15 carbon atoms, or a silylalkyl group represented by the formula (ii).

(Wherein, R ¹ to R ³ and a have the same meaning as in the above formula (i))
Component (B): an alkoxysilane having an epoxy group or an oxetane group represented by the following formula (iii) or a partial hydrolysis condensate thereof:
R ⁴ _b R ⁵ _c Si (OR ⁶ ) _4-b-c (iii)
(Wherein, R ⁴ and R ⁵ are both directly bonded to Si, R ⁴ is an organic group having 1 to 10 carbon atoms containing an epoxy group or an oxetane group, and R ⁵ is both an epoxy group and an oxetane group R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and b and c each represent a number of 0 <b ≦ 1 and 0 ≦ c ≦ 2. , B + c represents a number of 0 <b + c ≦ 2). The siloxane-based curable resin composition according to claim 1, wherein the ratio of component (A) to component (B) is 0.01 to 7 moles of component (A) per 1 mole of component (B). It is a hard-coating liquid which contains a curing catalyst as (C) component, and an organic solvent as (D) component, The siloxane type curable resin composition of Claim 1 characterized by the above-mentioned. Partial hydrolytic condensates of the following components (A) and (B), which have an epoxy equivalent of 200 to 4000 (g / eq), and photocationic polymerization initiators of the component (C ') And a surface-curing agent of component (E), a siloxane-based curable resin composition:
Component (A): an alkoxysilane having an isocyanurate ring structure represented by the following general formula (i) or a partial hydrolytic condensate thereof,

(Wherein, R ¹ represents an organic group having 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ represents an organic group having 1 to 6 carbon atoms, a Represents a number of 0 to 2, and X independently represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or a silylalkyl group represented by the formula (ii).

(Wherein, R ¹ to R ³ and a have the same meaning as in the above formula (i))
Component (B): an alkoxysilane having an epoxy group or an oxetane group represented by the following formula (iii) or a partial hydrolysis condensate thereof:
R ⁴ _b R ⁵ _C Si (OR ⁶ ) _4-b-c (iii)
(Wherein, R ⁴ and R ⁵ are both directly bonded to Si, R ⁴ is an organic group having 1 to 15 carbon atoms including an epoxy group or an oxetane group, and R ⁵ is both an epoxy group and an oxetane group R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and b and c each represent a number of 0 <b ≦ 1 and 0 ≦ c ≦ 2. , B + c represents a number of 0 <b + c ≦ 2).
(C ') component; photo cationic polymerization initiator (E) component; a surface conditioner comprising a fluorine compound, a dimethylsiloxane compound, or a modified product or derivative thereof. The siloxane-based curable resin composition according to claim 4, wherein the component (E) is a surface conditioner having a reactive group that forms a covalent bond with the partial hydrolytic condensate of the components (A) and (B). . A method for forming a hard coating film, comprising applying the siloxane-based curable resin composition according to claim 1 to a base layer or a substrate and drying the composition, and then curing the composition by active energy ray irradiation. The method for forming a hard coating film according to claim 6, further comprising heat treatment after curing. A cured film obtained by curing the siloxane-based curable resin composition according to claim 1 or 4. Siloxane-based curable resin containing a partial hydrolysis and condensation product which is a partial hydrolysis and condensation product of the following components (A) and (B) and has an epoxy equivalent of 200 to 4000 (g / eq), (C) component A laminate comprising a hard siloxane resin layer formed from a hard coating solution containing a curing catalyst as the component (D) and an organic solvent as the component (D), and a substrate layer:
Component (A): an alkoxysilane having an isocyanurate ring structure represented by the following general formula (i) or a partial hydrolytic condensate thereof,

(Wherein, R ¹ represents an organic group having 1 to 15 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ represents an organic group having 1 to 6 carbon atoms, a Represents a number of 0 to 2, and X independently represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or a silylalkyl group represented by the formula (ii).

(Wherein, R ¹ to R ³ and a have the same meaning as in the above formula (i))
Component (B): an alkoxysilane having an epoxy group or an oxetane group represented by the following formula (iii) or a partial hydrolysis condensate thereof:
R ⁴ _b R ⁵ _C Si (OR ⁶ ) _4-b-c (iii)
(Wherein, R ⁴ and R ⁵ are both directly bonded to Si, R ⁴ is an organic group having 2 to 15 carbon atoms including an epoxy group or an oxetane group, and R ⁵ is both an epoxy group and an oxetane group R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and b and c each represent a number of 0 <b ≦ 1 and 0 ≦ c ≦ 2. , B + c represents a number of 0 <b + c ≦ 2). The laminate according to claim 9, wherein the hard resin layer and the substrate are laminated via a resin layer composed of a single layer or a plurality of layers. The laminated body of Claim 9 laminated | stacked through the surface treatment layer of a base material. The laminate according to claim 10, wherein the resin layer is formed by using an acrylic resin, a urethane resin, a polyurea resin, an epoxy resin, a phenol resin, a siloxane resin, a polyimide resin, or a polyamideimide resin alone or in combination. The surface treatment layer of the substrate is formed by a treatment selected from anchor treatment, coupling agent treatment, ultraviolet ray irradiation treatment, plasma treatment, corona discharge treatment, blast treatment, brush treatment, polishing treatment, etching treatment, chemical conversion treatment, anodization The laminated body according to claim 11. The laminate according to claim 9, wherein the substrate is any of a thermoplastic resin, a curable resin, metal, wood, paper, glass and stone. A method of producing a laminate according to claim 9, wherein the hard coating solution is applied to a substrate, dried and then cured by active energy ray irradiation or heating. The laminate according to claim 15, wherein the hard coating solution is applied by any method selected from flow coating, roller coating, bar coating, spray coating, spin coating, curtain coating and dipping. Manufacturing method.