JP5265335B2 - Radical polymerizable composition - Google Patents

Description

  The present invention relates to a radically polymerizable composition that forms a film on the surface of, for example, a molded article made of wood, paper, glass, plastic, or the like, a film or a sheet, and a coating material that is made of this radically polymerizable composition.

A resin having polysiloxane in the main chain skeleton has been conventionally used as a coating material because it can form a cured product excellent in antifouling property, contamination removal property, surface hardness and the like.
Examples of the coating material include a photocurable (meth) acrylate resin, a photocurable polysiloxane urethane (meth) acrylate resin, a photocurable silicone block (meth) acrylate resin, and a photopolymerization initiator. It is known that the photocurable (meth) acrylate-based resin composition thus formed can form a film excellent in contamination removal (see, for example, Patent Document 1).
Further, in the presence of a polymer having a reactive double bond via an ether bond in the side chain of silicone, a specific hydrophilic vinyl monomer, a hydroxyl group-containing vinyl monomer, and a carboxyl group-containing vinyl monomer are copolymerized. It is known that the antifouling coating composition containing the produced graft copolymer is excellent in repaintability and storage stability and also in antifouling properties (see, for example, Patent Document 2). ).
In addition, the active energy ray-curable resin composition containing a polysiloxane skeleton, a polyfunctional urethane acrylate resin composed of an organic isocyanurate, and an unsaturated monomer has a high surface hardness and scratch resistance. It is known that an excellent film can be formed (see, for example, Patent Document 3).

On the other hand, a coating material having excellent antifouling properties is used for preventing, for example, adhesion of dirt due to finger touch and generation of scratches, specifically, touch panel parts such as small game machines and copiers. It is being considered for use in surface coating.
However, although the film formed using the resin composition described in Patent Documents 1 and 2 has good antifouling properties, it may not be sufficient in terms of scratch resistance. Moreover, although the film formed using the resin composition described in Patent Document 3 has good scratch resistance to some extent, it may not have practically sufficient antifouling properties.
Further, as the service life of copying machines and the like improves, antifouling properties are required to last for a long time. Further, in recent years, in addition to antifouling properties, even when dirt is attached to the surface of the coating, there is also a demand for a property that can remove dirt relatively easily by lightly wiping with a cloth or the like, so-called decontamination property. ing.
However, although the antifouling property and the decontamination property of the coating formed using the resin composition disclosed in Patent Documents 1 to 3 may have a relatively good effect if the coating is initially formed, There was a case where it decreased significantly with time.
JP 2003-192751 A Japanese Patent Laid-Open No. 7-278467 Japanese Patent Laid-Open No. 6-1819

  The problem to be solved by the present invention is, for example, a high hardness that can maintain excellent antifouling properties and decontamination properties against oily stains such as magic pens over a long period of time and has excellent scratch resistance. It is providing the radically polymerizable composition which can form a film.

That is, the present invention is derived from the urethane (meth) acrylate (A) having a structure derived from the polysiloxane (a) having a polyalkylene oxide chain in the side chain, and the polysiloxane (a) having the polyalkylene oxide chain in the side chain. Urethane (meth) acrylate (B) having no structure, (meth) acrylate (C) having a perfluoroalkyl group, and a crosslinking agent (D). ) Is an isocyanate group comprising a polysiloxane (a) having a polyalkylene oxide chain in the side chain and a polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule. It is formed by binding via the containing compound (b), and the urethane is added to the total amount of the urethane (meth) acrylate (B). Tan (meth) mass ratio of acrylate (A) [(A) / (B)] is in the range of 1 / 1-1 / 50, containing from 1 to 20 wt% of the urethane (meth) acrylate (A) and, the urethane (meth) acrylate (B) containing 20 to 50 wt%, said having a perfluoroalkyl group of (meth) acrylate (C) containing 10 to 50 mass%, the crosslinking agent (D) The polysiloxane (a) containing 10-50% by mass and having the polyalkylene oxide chain in the side chain has a hydroxyl equivalent in the range of 300-8000, and the polysiloxane having the polyalkylene oxide chain in the side chain (a ) Has a mass ratio of the polyalkylene oxide chain to the polysiloxane chain in the range of 1 / 0.05 to 1/110, and the crosslinking agent (D) contains 3 or more (meth) acrylates. Providing a radical polymerizable composition, characterized by having a Relate group.

According to the radically polymerizable composition of the present invention, it is possible to form a coating having excellent antifouling properties and scratch resistance while being able to maintain antifouling properties and decontamination properties for a long period of time. Touch panels, CDs, DVDs, Blu-ray discs, displays used in game machines, mobile phones, car navigation systems, personal computers, digital cameras, ATMs, ticket machines, POS terminals, handy terminals, FA devices, copiers, etc. Surface layer of magnetic recording media such as HD-DVD, roof of buildings, surface coatings such as outer walls and waterproof layers, surface layers of bathtubs, bathrooms, wash bowls, mirrors, kitchen sinks, toilet bowls, cameras, videos It can be used as a coating material for the surface layer of plastic lenses such as cameras and glasses.
Further, according to the radically polymerizable composition of the present invention, curing can be performed by any curing method such as curing by active energy rays, heat curing by using a peroxide, or room temperature curing by using a peroxide and a reducing agent. Therefore, a curing method according to the application can be adopted. In particular, in flat panel applications, curing with active energy rays is preferable because thinning and high hardness are possible.

The best mode of the radically polymerizable composition of the present invention will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

  The radical polymerizable composition of the present invention comprises a urethane (meth) acrylate (A) having a structure derived from a polysiloxane (a) having a polyalkylene oxide chain in the side chain, a polysiloxane having a polyalkylene oxide chain in the side chain ( a) Urethane (meth) acrylate (B) having no derived structure, (meth) acrylate (C) having a perfluoroalkyl group, and a crosslinking agent (D).

  The urethane (meth) acrylate (A) constituting the radical polymerizable composition of the present invention comprises a polysiloxane (a) having a polyalkylene oxide chain in the side chain, a hydroxyl group in the molecule and at least one polymerizable unsaturated. A polymerizable monomer (d) having a double bond is bonded through an isocyanate group-containing compound (b).

  The urethane (meth) acrylate (A) is derived from the polysiloxane (a) having a polyalkylene oxide chain in the side chain from the viewpoint of forming a film capable of maintaining excellent antifouling property, contamination removal property and scratch resistance for a long period of time. It is essential to have the structure of

  Further, as urethane (meth) acrylate (A), it is necessary to use one having two or more (meth) acryloyl groups that can contribute to the formation of a cured film, but it has high hardness and excellent scratch resistance. From the viewpoint of forming a coated film, those having two or more (meth) acryloyl groups are preferably used, and those having 2 to 5 (meth) acryloyl groups are more preferably used.

  The urethane (meth) acrylate (A) is a structure derived from polysiloxane (a) by reacting, for example, polysiloxane (a) having a polyalkylene oxide chain in the side chain with an isocyanate group-containing compound (b). And a compound (c) having an isocyanate group, and reacting the compound (c) with a polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule. Can be generated.

  Specifically, for example, the polysiloxane (a) having a polyalkylene oxide chain in the side chain and the isocyanate group-containing compound (b), preferably the isocyanate group (NCO) of the isocyanate group-containing compound (b) And the equivalent ratio (NCO / active hydrogen atom-containing group) of the active hydrogen atom-containing group such as a hydroxyl group of the polysiloxane (a) having a polyalkylene oxide chain in the side chain is 1 to 2.5. To produce the compound (c), and then the compound (c) and a polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule. Can be made to react.

The polysiloxane (a) having a polyalkylene oxide chain in the side chain will be described.
In the radically polymerizable composition of the present invention, as the polysiloxane (a) having a polyalkylene oxide chain in the side chain, a polyalkylene oxide chain comprising a ring-opening reaction product of an alkylene oxide is added to a main chain comprising a polysiloxane chain. It is important to use a side chain graft polymerized in a pendant form.
For example, when a block copolymer consisting of a polyalkylene oxide chain and a polysiloxane chain is used in place of the polysiloxane (a) having a polyalkylene oxide chain in the side chain, a film having good decontamination is formed. However, it is difficult to form a film having high hardness and excellent scratch resistance.
On the other hand, if the urethane (meth) acrylate (A) produced by using the polysiloxane (a) having a polyalkylene oxide chain in the side chain is used, it is excellent in decontamination and scratch resistance and has a high hardness film. A radically polymerizable composition that can be formed is obtained.

Since the polyalkylene oxide chain relaxes the crystallinity of the polysiloxane chain, the resulting urethane (meth) acrylate (A) is improved in compatibility with (meth) acrylate (C) having a perfluoroalkyl group. It is necessary from.
In addition, the urethane (meth) acrylate which consists only of a polysiloxane chain is not compatible with the other component which comprises the radically polymerizable composition of this invention.

As the polyalkylene oxide chain, for example, polyalkylene oxides such as polyethylene oxide, polypropylene oxide, polybutylene oxide and the like can be used, and preferably polyethylene oxide is used.
As the polyalkylene oxide, an adduct of 2 to 15 moles of alkylene oxide is preferably used.

  As the polysiloxane chain, for example, polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polyethylphenylsiloxane, polydiphenylsiloxane, and the like can be used. Among these, using a polysiloxane chain composed of a silicon atom to which two or more alkyl groups or phenyl groups are bonded improves the decontamination property and stabilizes the urethane (meth) acrylate (A). It is more preferable from the viewpoint of production, and it is particularly preferable to use polydimethylpolysiloxane.

The polysiloxane (a) having a polyalkylene oxide chain in the side chain preferably has an active hydrogen atom-containing group that is reactive with the isocyanate group of the isocyanate group-containing compound (b) described later.
Here, the active hydrogen atom-containing group is preferably a hydroxyl group. The hydroxyl group may be directly bonded to a silicon atom or the like constituting a polysiloxane chain as a main chain, but is preferably bonded to a carbon atom or the like constituting a polyalkylene oxide chain as a side chain.

As the polysiloxane (a) having a polyalkylene oxide chain in the side chain, one having a hydroxyl equivalent of 300 to 8000 is preferably used, and one having 700 to 3000 is more preferable.
By using the polysiloxane (a) having a hydroxyl group equivalent in the above range and having a polyalkylene oxide chain in the side chain, a radically polymerizable composition capable of forming a film having excellent decontamination can be obtained.

Moreover, as polysiloxane (a) having a polyalkylene oxide chain in the side chain, a polyalkylene oxide chain part (hereinafter referred to as “polyalkylene oxide chain part”) and a polysiloxane chain part (hereinafter referred to as “polyalkylene oxide chain part”). It is preferable to use a material having a mass ratio of 1 / 0.05 to 1/110, and a material having a mass ratio of 1/2 to 1/50. It is more preferable to use a material in the range of 1/2 to 1/5.
By using a polysiloxane (a) having a polyalkylene oxide chain in the side chain, in which the mass ratio of the polyalkylene oxide chain part to the polysiloxane chain part is within the above range, the polyalkylene oxide chain is used as the side chain. A radically polymerizable composition capable of forming a film excellent in solubility in the (meth) acrylate (C) having a perfluoroalkyl group of the polysiloxane (a) having an excellent contamination removal property is obtained.

  The polysiloxane (a) having a polyalkylene oxide chain in the side chain may have other molecular chains in addition to the polyalkylene oxide chain part and the polysiloxane chain part. For example, the polyalkylene oxide chain The part and the polysiloxane chain part may be bonded via other molecular chains or chemical bonds.

  Specific examples of the polysiloxane (a) having a polyalkylene oxide chain in the side chain include those having a structure represented by the following general formula (I).

However, in the above general formula (I), R ₁ represents an alkylene group having 1 to 6 carbon atoms, R ₂ and R ₃ each independently represents an alkylene group having 2 to 4 carbon atoms, R ₄ each independently represents an alkyl group having 1 to 8 carbon atoms or a phenyl group. Moreover, in said general formula (I), a and b represent the integer of 1-8 each independently, and m and n represent the integer of 1-10 each independently.

  Examples of the commercially available polysiloxane (a) having a polyalkylene oxide chain in the side chain include FZ-2191 and SH-3771 manufactured by Toray Dow Corning, KF353A manufactured by Shin-Etsu Chemical Co., Ltd. It is not limited to these.

Next, the isocyanate group containing compound (b) used for the production | generation of urethane (meth) acrylate (A) is demonstrated.
The isocyanate group-containing compound (b) refers to a compound having two or more isocyanate groups in the molecule. For example, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, 2,4- Tolylene diisocyanate, its isomer or a mixture of these isomers, 4,4-diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”). ), Diisocyanates such as xylylene diisocyanate and norbornene diisocyanate, adducts of diisocyanates with trihydric or higher aliphatic polyhydric alcohols such as trimethylolpropane, isocyanurate structures which are trimers of diisocyanate, diisocyanate and water A burette produced by the above reaction or polymeric MDI is used.

  The isocyanate group-containing compound (b) is an aliphatic isocyanate group-containing compound having two or more isocyanate groups in the molecule from the viewpoint of preventing discoloration of the cured product of the radical polymerizable composition of the present invention over time. From the viewpoint of improving the surface hardness and heat resistance of the coating obtained by curing the radical polymerizable composition of the present invention, and improving the compatibility of the radical polymerizable composition of the present invention, the cyclohexane ring is preferably used. It is more preferable to use an isocyanate group-containing compound having a norbornene ring.

Next, the polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule, which is used for producing the urethane (meth) acrylate (A), will be described.
The polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule increases the hardness of the film obtained by curing the radically polymerizable composition of the present invention. It is an essential component from the viewpoint of imparting the effect of improving the scratch resistance.

  The polymerizable unsaturated double bond of the polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule is obtained by curing the radically polymerizable composition of the present invention. From the viewpoint of further improving the surface hardness of the resulting coating and imparting excellent scratch resistance to the coating, it is preferably in the range of 2 to 5.

Examples of the polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylates and their ε-caprolactone adducts, ethylene oxide adducts, propylene oxide adducts, ε-caprolactam adducts, trimethylolpropane di (meth) acrylate, trimethylolpropane methacrylate acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta One or more selected from the group of erythritol hexa (meth) acrylate is used.
Among these, one or more selected from the group of trimethylolpropane di (meth) acrylate, trimethylolpropane methacrylate acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate should be used. However, it is particularly preferable from the viewpoint of further improving the surface hardness of the coating obtained by curing the radically polymerizable composition of the present invention and imparting excellent scratch resistance to the coating.

  Further, when the urethane (meth) acrylate (A) is produced, a hydroxyl group and at least one polymerizable unsaturated double bond are included in the molecule for the purpose of preventing the curing of the radical polymerizable composition of the present invention by air. In addition to the polymerizable monomer (d), a hydroxyl group-containing allyl ether compound may be used.

  Examples of the hydroxyl group-containing allyl ether compound include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, and tripropylene glycol. Monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, Many types such as glyceryl diallyl ether and pentaerythritol triallyl ether Allyl ether compounds alcohol is used, it is preferable to use allyl ether compound having one hydroxyl group among them.

Urethane (meth) acrylate (A) can be produced by the following two-stage reaction process.
In the first stage reaction step, 1 equivalent of the hydroxyl group of the polysiloxane (a) having a polyalkylene oxide chain in the side chain and 2 equivalents or more of the isocyanate group of the isocyanate group-containing compound (b) are reacted with each other. This is a step of producing a compound (c) having an isocyanate group and a structure derived from polysiloxane (a) having an alkylene oxide chain in the side chain.

This first stage reaction step is preferably carried out in a range of room temperature to about 100 ° C. in a nitrogen atmosphere.
In addition, the reaction step in the first stage can be carried out in the absence of a solvent. However, if necessary, an organic solvent or a (meth) acrylate (C) having a perfluoroalkyl group described later is used as a solvent. You can also.

In the first stage reaction step, a catalyst may be used as necessary.
Examples of the catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate and tetraethyl titanate, organotin compounds such as tin octylate, dibutyltin oxide and dibutyltin dilaurate, and further stannous chloride and stannous bromide. Well-known catalysts such as acids and alkalis such as stannous iodide can be used.
The amount of these catalysts added is preferably 10 to 10,000 ppm with respect to the total amount of the polysiloxane (a) having a polyalkylene oxide chain in the side chain and the isocyanate group-containing compound (b).

  In the second stage reaction step, the compound (c) produced in the first stage reaction step has a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule. This is a step of reacting the hydroxyl group of the functional monomer (d).

  The polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule has a hydroxyl group and at least one in the molecule with respect to 1 equivalent of the isocyanate group of the compound (c). The polymerizable monomer (d) having a polymerizable unsaturated double bond is preferably used in the range of 1 to 1.5 equivalents of a hydroxyl group.

This second-stage reaction step is preferably performed in the range of room temperature to about 90 ° C.
In addition, the second-stage reaction step can be performed in the absence of a solvent, but if necessary, an organic solvent or a (meth) acrylate (C) having a perfluoroalkyl group described later is used as a solvent. You can also.

In the second-stage reaction step, the same catalyst as that used in the first-stage reaction step can be used as necessary.
Moreover, in order to suppress radical polymerization of the polymerizable unsaturated double bond of the polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule, as necessary A radical polymerization inhibitor can be used.

As the radical polymerization inhibitor, for example, hydroquinone monomethyl ether, dt-butyl hydroquinone, pt-butyl catechol, phenothiazine and the like can be used.
The amount of the radical polymerization inhibitor used is 10 to 10,000 ppm with respect to the total charged amount of the polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule. It is preferable.

It is preferable that content of urethane (meth) acrylate (A) exists in the range of 1-20 mass% with respect to the whole quantity of the radically polymerizable composition of this invention.
In addition, the mass ratio [(A) / (B)] of the urethane (meth) acrylate (A) to the total amount of the urethane (meth) acrylate (B) is within a range of 1/1 to 1/50. It is more preferable from the viewpoint of forming a high-hardness film excellent in removability and scratch resistance, and particularly preferably in the range of 1/10 to 1/50.

Next, urethane (meth) acrylate (B) will be described.
Urethane (meth) acrylate (B) is the same as urethane (meth) acrylate (A) except that it does not have a structure derived from polysiloxane (a) having a polyalkylene oxide chain in the side chain. , A reaction product of an isocyanate group-containing compound (b) and a polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule.

Therefore, urethane (meth) acrylate (B) is the same as the reaction step in the production of urethane (meth) acrylate (A) without using polysiloxane (a) having a polyalkylene oxide chain in the side chain. The isocyanate group-containing compound (b) and the polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule are, for example, from room temperature to 90 in a nitrogen atmosphere. It can produce | generate by making it react in presence of the (meth) acrylate (C) which has a perfluoroalkyl group in the range of about (degreeC) under no solvent, an organic solvent.
As the isocyanate group-containing compound (b) used for the production of the urethane (meth) acrylate (B) and the polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule, The thing similar to what is used for the production | generation of said urethane (meth) acrylate (A) is used.

Moreover, as urethane (meth) acrylate (B), what was produced | generated separately from urethane (meth) acrylate (A) is used normally, but by adjusting the preparation ratio of a raw material, urethane (meth) acrylate ( It is preferable from the viewpoint of improving the production efficiency to use a product generated together with A).
Specifically, when producing the urethane (meth) acrylate (A), the amount of the polysiloxane (a) having a polyalkylene oxide chain in the side chain is used in the isocyanate group-containing compound (b) and in the molecule. By using excessively the polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond, (A) and (B) can be produced in a lump.

  The content of the urethane (meth) acrylate (B) is in the range of 20 to 50% by mass with respect to the total amount of the radical polymerizable composition of the present invention, so that a film having high hardness and excellent scratch resistance can be obtained. It is more preferable from the viewpoint of formation.

Next, (meth) acrylate (C) having a perfluoroalkyl group will be described.
The (meth) acrylate (C) having a perfluoroalkyl group is an essential component from the viewpoint of imparting contamination removal persistence to a film obtained by curing the radically polymerizable composition of the present invention.
Although the coating film containing no (meth) acrylate (C) having a perfluoroalkyl group has a relatively good antifouling property at the initial stage of the film formation, it is possible to prevent the deterioration with time by repeated contamination and removal. May cause a decrease in soiling.
On the other hand, since the radically polymerizable composition of the present invention contains a (meth) acrylate (C) having a perfluoroalkyl group, it is possible to maintain excellent antifouling properties over a long period of time.

Examples of the (meth) acrylate (C) having a perfluoroalkyl group include an acrylate ester or a methacrylate ester of an alcohol having a fluorinated alkyl group and / or an alkylene group, and a hydrogen atom of the alkyl group or the alkylene group. Acrylic ester or methacrylic ester of alcohol in which a part or all of them are substituted with fluorine and the total number of carbon atoms in one molecule is 1 to 30 is used. .
Specifically, compounds represented by the following general formulas (II) to (V) are used.

However, in said general formula (II)-(V), m represents the integer of 1-18 independently, and n represents the integer of 0-18 independently. In the above chemical formulas (II) to (V), R is H or CH ₃ CO, and X is H or CH ₃ .

  Among the (meth) acrylates (C) having a perfluoroalkyl group represented by the above general formula, in particular, 2,2,2-trifluoroethyl (meth) acrylate may be used as a urethane (meth) acrylate (A ) And the radical polymerizability, and the coating obtained by curing the radical polymerizable composition of the present invention can be imparted with a practically sufficient long-lasting decontamination property. preferable.

  The content of the (meth) acrylate (C) having a perfluoroalkyl group is in the range of 10 to 50% by mass with respect to the total amount of the radically polymerizable composition of the present invention. It is preferable from the viewpoint of forming a film excellent in sustainability and obtaining a radical polymerizable composition having good coating workability.

Next, a crosslinking agent (D) is demonstrated.
The crosslinking agent (D) is an essential component from the viewpoint of increasing the crosslinking density of the film obtained by curing the radical polymerizable composition of the present invention, further improving the surface hardness, and imparting excellent scratch resistance. . In addition, increasing the crosslinking density of the coating prevents the coating from absorbing contaminants, so that the crosslinking agent (D) is an essential component from the viewpoint of further improving the antifouling property and the decontamination durability. is there.

As the crosslinking agent (D), for example, it is preferable to use (meth) acrylate having two or more (meth) acrylate groups, and 1,3-butanediol di (meth) acrylate, 1,4-butanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol One or more members selected from the group of Rupenta (meth) acrylate is used.
In particular, it is more preferable to use pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like from the viewpoint of forming a high-hardness film excellent in scratch resistance.

  The content of the crosslinking agent (D) is in the range of 10 to 50% by mass with respect to the total amount of the radical polymerization composition of the present invention, and has excellent scratch resistance, antifouling property and decontamination property. This is preferable from the viewpoint of forming a long-lasting film and obtaining a radically polymerizable composition having good film forming workability.

The radically polymerizable composition of the present invention includes, for example, urethane (meth) acrylate (A), urethane (meth) acrylate (B), (meth) acrylate (C) having a perfluoroalkyl group, and a crosslinking agent (D ) Can be produced by batch mixing and stirring at a temperature of 60 ° C. or lower.
Moreover, when using the (meth) acrylate (C) which has a perfluoroalkyl group as a solvent at the time of producing | generating a urethane (meth) acrylate (A) and a urethane (meth) acrylate (B), it has a perfluoroalkyl group. (Meth) acrylate (C) may be mixed in advance with urethane (meth) acrylate (A) or urethane (meth) acrylate (B).
Also, when urethane (meth) acrylate (A) and urethane (meth) acrylate (B) are produced together, mixing and stirring the mixture and (meth) acrylate (C) having a perfluoroalkyl group Thus, the radically polymerizable composition of the present invention can be produced.

  The radically polymerizable composition of the present invention can be cured by any curing method such as curing by active energy rays, heat curing by using a peroxide, or room temperature curing by using a peroxide and a reducing agent. However, curing with active energy rays is most preferable from the viewpoint of forming a coating with higher hardness.

When the radically polymerizable composition of the present invention is cured by active energy rays, it is preferable to use a photopolymerization initiator as a curing agent.
Examples of the photopolymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, Thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxy Cyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone Which acetophenones; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide, acylphosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, 1,7-bisacridinylheptane, 9-phenylacridine One or more selected from the group is used.

  When the radically polymerizable composition of the present invention is cured by an active energy ray, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, together with a photopolymerization initiator as necessary, Known photosensitizers such as ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate and 4-dimethylaminoacetophenone are used.

  When the radical polymerizable composition of the present invention is cured by heating using a peroxide, examples of the curing agent include diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketones. Peroxides such as peroxides, peroxyketals, alkyl peresters, and carbonates are used.

  In addition, when the radically polymerizable composition of the present invention is cured at room temperature, the above-described peroxide and an organic metal salt such as cobalt naphthenate and cobalt octenoate as a curing accelerator, dimethylaniline, diethylaniline, paratoluidine, etc. Used in combination with an aromatic amine compound.

  The compounding amount of the curing agent is preferably in the range of 0.1 to 10 parts by mass, and in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the radical polymerizable composition of the present invention. Is more preferable.

Moreover, you may add a polymerization inhibitor to the radically polymerizable composition of this invention as needed.
As the polymerization inhibitor, for example, trihydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, toluhydronone, p-tert-butylcatechol, 2,6-tert-butyl-4-methylphenol and the like are used.
The blending amount of the polymerization inhibitor is preferably 10 to 1,000 ppm in the radical polymerizable composition of the present invention.

  In addition, the radically polymerizable composition of the present invention includes generally known unsaturated polyester resins, epoxy acrylate resins, polyurethane resins, acrylic resins, alkyd resins, urea within the range that does not impair the effects of the present invention. Resins, melamine resins, polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyester resins, saturated polyethers, celluloses and their derivatives, fats and oils, and many other common natural and synthetic polymers Compounds can also be added.

Since the radically polymerizable composition of the present invention is excellent in adhesion to various substrates, it can be used as a coating material for the purpose of surface protection of various substrates.
As the base material, for example, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polyvinyl alcohol, hard vinyl chloride, soft vinyl chloride, ABS resin, unsaturated polyester resin, FRP made of vinyl ester resin or epoxy resin, etc. are known. Plastic, wood, metal, concrete, asphalt, glass, paper, etc. are used.
The composite having a coating formed by applying the coating material of the present invention to the surface of the base material and curing it by the above-described method can maintain the contamination property and the decontamination property for a long period of time, and is scratch resistant. For example, it can be used as an optical material such as various displays, touch panels, magnetic recording media, building exterior materials, and plastic lenses.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.

“Synthesis Example 1”
Urethane (meth) acrylate (A-1) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain and urethane (meth) having no structure derived from polysiloxane having a polyalkylene oxide chain in the side chain Preparation of Mixture (I) with Acrylate (B-1) A polyalkylene oxide chain is side-chained into a 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 37 parts by mass (0.03 mol) of polysiloxane (trade name: FZ-2191, hydroxyl value 45.9, manufactured by Toray Dow Corning) is added, and 206 parts by mass (1 mol) of norbornene diisocyanate is added to suppress heat generation. The reaction was carried out at 80 ° C. for 2 hours.

After confirming that the equivalent of the isocyanate group was 123, which was almost the same as the theoretical value when all the hydroxyl groups of the polysiloxane reacted with the isocyanate group, it was cooled to 50 ° C. and 375 parts by mass of pentaerythritol triacrylate ( 1.26 mol) and 122 parts by mass (1.05 mol) of 2-hydroxyethyl acrylate were added, 0.02 parts by mass of tin catalyst was added as a reaction promoting catalyst, and the mixture was reacted at 90 ° C. for 7 hours in an air atmosphere.
Then, after the unreacted isocyanate group becomes 0.3% by mass or less, urethane (meth) having a structure derived from polysiloxane having a polyalkylene oxide chain in the side chain is added by adding 0.1 part by mass of hydroquinone. Mass ratio of acrylate (A-1) and urethane (meth) acrylate (B-1) having no polysiloxane-derived structure having a polyalkylene oxide chain in the side chain [(A-1) / (B- 1)] was obtained as 3/37.

“Synthesis Example 2”
Urethane (meth) acrylate (A-2) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain, and urethane (meth) having no structure derived from a polysiloxane having a polyalkylene oxide chain in the side chain Preparation of mixture (II) with acrylate (B-2) A polyalkylene oxide chain is side-chained to a 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 24 parts by mass (0.03 mol) of polysiloxane (trade name: FZ-2191, hydroxyl value 45.9, manufactured by Toray Dow Corning) is added, 144 parts by mass ( 0.65 mol) of isophorone diisocyanate is added, The reaction was carried out at 80 ° C. for 2 hours while suppressing the exotherm.

The equivalent of the isocyanate group becomes 132, which is almost the same as the theoretical value when all the hydroxyl groups of the polysiloxane have reacted with the isocyanate group, and then stabilized, cooled to 50 ° C., and 1619 parts by mass of dipentaerythritol pentaacrylate ( 3.1 mol), 0.08 parts by mass of tin catalyst was added as a reaction promoting catalyst, and the mixture was reacted at 90 ° C. for 7 hours in an air atmosphere.
Then, after the unreacted isocyanate group becomes 0.3% by mass or less, by adding 0.2 part by mass of hydroquinone, urethane (meth) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain. Mass ratio of acrylate (A-2) and urethane (meth) acrylate (B-2) having no polysiloxane-derived structure having a polyalkylene oxide chain in the side chain [(A-2) / (B- 2)] was obtained as 2/38.

“Synthesis Example 3”
Urethane (meth) acrylate (A-3) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain and urethane (meth) having no structure derived from a polysiloxane having a polyalkylene oxide chain in the side chain Preparation of Mixture (III) with Acrylate (B-3) Polyalkylene oxide chain was side-chained into a 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 55.5 parts by mass (0.045 mol) of polysiloxane (trade name: FZ-2191, hydroxyl value 45.9, manufactured by Toray Dow Corning Co., Ltd.) and 309 parts by mass (1.5 mol) of norbornene diisocyanate are added. The reaction was carried out at 80 ° C. for 2 hours while suppressing the exotherm.

The equivalent of the isocyanate group becomes 123, which is almost the same as the theoretical value when all the hydroxyl groups of the polysiloxane have reacted with the isocyanate group. After stabilization, the mixture is cooled to 50 ° C. and 365 parts by mass (3.15 mol) of 2-hydroxyethyl acrylate is obtained. In addition, 0.02 parts by mass of a tin catalyst was added as a reaction promoting catalyst, and the reaction was carried out at 90 ° C. for 7 hours in an air atmosphere.
Then, after the unreacted isocyanate group becomes 0.3% by mass or less, by adding 0.2 part by mass of hydroquinone, urethane (meth) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain. Mass ratio of acrylate (A-3) and urethane (meth) acrylate (B-3) having no polysiloxane-derived structure having a polyalkylene oxide chain in the side chain [(A-3) / ( B − 3)] was obtained as 3/37.

“Synthesis Example 4”
Urethane (meth) acrylate (A-4) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain and urethane (meth) having no structure derived from polysiloxane having a polyalkylene oxide chain in the side chain Preparation of mixture (IV) with acrylate (B-4) A polyalkylene oxide chain is side-chained into a 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser. 37 parts by mass (0.03 mol) of polysiloxane (trade name: FZ-2191, hydroxyl value 45.9, manufactured by Toray Dow Corning Co.), and 168 parts by mass (1.0 mol) of hexamethylene diisocyanate were added. The reaction was carried out at 80 ° C. for 2 hours while suppressing the exotherm.

The equivalent of the isocyanate group becomes 104, which is almost the same as the theoretical value when all the hydroxyl groups of the polysiloxane have reacted with the isocyanate group, and after stabilization, the mixture is cooled to 50 ° C. and 2501 parts by mass of dipentaerythritol pentaacrylate ( 4.77). mol), 0.08 parts by mass of tin catalyst was added as a reaction promoting catalyst, and the mixture was reacted at 90 ° C. for 7 hours in an air atmosphere.
Then, after the unreacted isocyanate group becomes 0.3% by mass or less, by adding 0.2 part by mass of hydroquinone, urethane (meth) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain. Mass ratio [(A- 4 ) / (B-) of acrylate (A-4) and urethane (meth) acrylate (B-4) having no polysiloxane-derived structure having a polyalkylene oxide chain in the side chain. 4 )] was obtained as a mixture (IV) of 1.7 / 38.3.

“Comparative Synthesis Example 1”
Preparation of urethane (meth) acrylate (V) having no polysiloxane-derived structure having a polyalkylene oxide chain in the side chain A capacity of 2 liters equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser A 4-necked flask was charged with 206 parts by mass (1 mol) of norbornene diisocyanate, 375 parts by mass (1.26 mol) of pentaerythritol triacrylate, and 122 parts by mass (1.05 mol) of 2-hydroxyethyl acrylate, and a reaction promoting catalyst. 0.02 parts by mass of a tin catalyst was added and reacted at 90 ° C. for 7 hours in an air atmosphere.
And after the unreacted isocyanate group becomes 0.3 mass% or less, by adding 0.1 part by mass of hydroquinone, urethane having no polysiloxane-derived structure having a polyalkylene oxide chain in the side chain ( A (meth) acrylate (V) was obtained.

"Examples 1-8 and Comparative Examples 1-4"
Mixing and stirring the above mixtures (I) to (V), the (meth) acrylate having a perfluoroalkyl group described in Tables 1 and 2 and the crosslinking agent according to the composition ratios described in Tables 1 and 2 By doing this, the radically polymerizable composition of Examples 1-8 and Comparative Examples 1-4 was prepared.

"Film preparation method"
In each of the radical polymerizable compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 4, 5% by mass of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was dissolved on a glass substrate with a thickness of about 10 μm. The film is coated in such a manner that, in an air atmosphere, the surface to be coated is irradiated with ultraviolet rays using one UV lamp 120W metal halide (UV irradiation amount: 1000 mJ / cm ^{2 1} pass) to cure the radical polymerizable composition. Formed.

[Method for evaluating film performance]
The performance of the obtained coating was evaluated by the following method.

[Appearance of coating film]
The surface of the obtained film was visually observed to judge the transparency of the film.
The coating components that were not compatible and whitened were judged to be “incompatible”.

[Anti-fouling]
Characters were written on the surface of the film using an oil-based magic (Pentel pen, oil-based, medium-character black), and the appearance of the surface of the film after the characters were wiped with a dry cloth was visually observed.
“O” indicates that no oil-based magic ink remains on the surface of the film, “Δ” indicates that some of the oil-based magic ink remains, but “△” indicates that it is practically usable, and more than half of the oil-based magic ink remains. What was had was evaluated as "x".

[Sustainability of antifouling and decontamination]
Write the letters using oily magic (Pentel pen, oily, middle black) on the surface of the film, and repeat the process of wiping the letters with a dry cloth at the same location on the film surface. After wiping, the number of times until the characters did not disappear was examined to determine how long the antifouling property and decontamination property were maintained.
The case where the number of times until the character disappears was 50 times or more was evaluated as being able to maintain excellent antifouling property for a long period of time and not to deteriorate the antifouling property by wiping off the dirt.

[surface hardness]
The pencil hardness of the coating surface was measured according to JIS K5600 “Scratch hardness (pencil method): 1000 g load”.
Those having a pencil hardness of 4H or more were evaluated as having excellent surface hardness.

[Abrasion resistance]
The surface appearance of the coating was evaluated when 10 reciprocating rubs were performed with a 250 g load using steel wool # 0000.
“1” indicates no scratches on the coating surface, “2” indicates slight scratches on part of the coating surface, “3” indicates that noticeable scratches are observed on part of the coating surface, A sample having a markedly conspicuous scratch on the surface was evaluated as “4”.

Claims (7)

Urethane (meth) acrylate (A) having a structure derived from polysiloxane (a) having a polyalkylene oxide chain in the side chain, no structure derived from polysiloxane (a) having a polyalkylene oxide chain in the side chain Containing urethane (meth) acrylate (B), (meth) acrylate (C) having a perfluoroalkyl group, and a crosslinking agent (D),
The urethane (meth) acrylate (A) comprises the polysiloxane (a) having the polyalkylene oxide chain in the side chain, and a polymerizable monomer having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule. The body (d) is bonded through the isocyanate group-containing compound (b),
The mass ratio [(A) / (B)] of the urethane (meth) acrylate (A) to the total amount of the urethane (meth) acrylate (B) is in the range of 1/1 to 1/50,
(Meth) acrylate (C) containing 1 to 20% by mass of the urethane (meth) acrylate (A), 20 to 50% by mass of the urethane (meth) acrylate (B), and having the perfluoroalkyl group. 10 to 50% by mass, 10 to 50% by mass of the crosslinking agent (D),
The hydroxyl group equivalent of the polysiloxane (a) having the polyalkylene oxide chain in the side chain is in the range of 300 to 8000,
The polysiloxane (a) having the polyalkylene oxide chain in the side chain has a mass ratio of the polyalkylene oxide chain to the polysiloxane chain in the range of 1 / 0.05 to 1/110,
The said crosslinking agent (D) has a 3 or more (meth) acrylate group, The radically polymerizable composition characterized by the above-mentioned.  The polysiloxane (a) having a polyalkylene oxide chain in the side chain is obtained by graft polymerization of a side chain composed of a polyalkylene oxide chain composed of an adduct of 2 to 15 moles of alkylene oxide on a main chain composed of a polysiloxane chain. The radical polymerizable composition according to claim 1.  2. The radical polymerizable composition according to claim 1, wherein the polysiloxane (a) having a polyalkylene oxide chain in the side chain is composed of a silicon atom to which two or more alkyl groups or phenyl groups are bonded.  The urethane (meth) acrylate (B) comprises the isocyanate group-containing compound (b) and a polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond in the molecule. The radically polymerizable composition according to claim 1, which is a reaction product.  2. The radical polymerizable composition according to claim 1, wherein the crosslinking agent (D) comprises one or more selected from the group consisting of pentaerythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate.  A coating material comprising the radically polymerizable composition according to any one of claims 1 to 5.  The composite_body | complex which has the film formed using the coating | covering material of Claim 6 on the base-material surface.