JP5315829B2 - Curable hard coat agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable type coating material composition comprising a multifunctional (meth)acrylate, having excellent hardness, scratch resistance, further small curls, and even excellent flex resistance of a cured film, and excellent particularly as a hard coating agent. <P>SOLUTION: The curable type coating material composition comprises the following (meth)acrylate mixture: &cir; the (meth)acrylate mixture: a mixture comprising pentaerythritol tri(meth)acrylate (hereinafter referred to as triester); pentaerythritol tetra(meth)acrylate (hereinafter referred to as tetraester); and a compound in which the hydroxyl group of the triester is subjected to the Michael addition to the (meth)acryloyl group of the tetraester (hereinafter referred to as the compound M) in an area ratio of triester:tetraester:compound M=(0.1-2.0):100:(15.0-50.0) which is the area ratio when the area of the tetraester is 100 measured by liquid chromatography under specific conditions. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention, by irradiation of an active energy ray, or relates curable hard coat agent composition curable by heating, the composition of the present invention are useful in the hard coat application is a coating of plus chip click And can be used in the technical field in which they are used.
In the present specification, an acryloyl group and / or a methacryloyl group are represented as a (meth) acryloyl group, an acrylate and / or methacrylate as a (meth) acrylate, and acrylic acid and / or methacrylic acid as (meth) acrylic acid. .

  In general, plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and ABS resin are excellent in light weight, easy processability, impact resistance, and the like, and are used in various applications.

  However, these plastic products are susceptible to scratches on the surface, and have the disadvantages of impairing the transparency or appearance of the raw material resin. In many fields where wear resistance is required, hard coating is applied to the surface. Is given. As hard coat coating agents (hereinafter referred to as hard coat agents) used for the hard coat, acrylic hard coat agents, silane hard coat agents, acrylic-silicon hard coat agents, and the like are known.

  Among these, the acrylic hard coat agent contains (meth) acrylate, and can be cured by irradiation with active energy rays such as ultraviolet rays. There are many advantages such as a resin cost that is ¼ to の that of a silane-based hard coat agent, and it is widely used in this field.

  In conventional acrylic hard coating agents, (meth) acrylate having two or more (meth) acryloyl groups in one molecule [hereinafter referred to as polyfunctional (meth)] in order to impart hardness and abrasion resistance to the cured film. In many cases, polyfunctional (meth) acrylates having 4 or more (meth) acryloyl groups in one molecule are blended (for example, Patent Documents 1 to 3).

However, the acrylic hard coating agent containing polyfunctional (meth) acrylate has a cured film that is excellent in hardness and abrasion resistance. It was often insufficient.
In particular, in recent years, display bodies such as liquid crystal displays, plasma displays, and touch panel displays, which are provided with a film having a hard coat agent as a protective layer on the surface, are rapidly spreading. In addition to scratch resistance, there is a demand for a film that has low shrinkage during curing, small film curl, and excellent flex resistance.

  The present inventors are a curable coating composition containing a polyfunctional (meth) acrylate, in which a cured film is excellent in hardness and scratch resistance, and further has low curl and excellent flex resistance. In order to find a curable composition that is excellent as a coating agent, intensive studies were conducted.

Japanese Patent Publication No. 7-107140 (Claims) JP 2007-131837 A (Claims) JP 2007-231138 A (Claims)

  In order to solve the above problems, the present inventors have added pentaerythritol tri (meth) acrylate (tri), pentaerythritol tetra (meth) acrylate (tetra) and specific Michael addition as polyfunctional (meth) acrylate. The present inventors have found that a composition containing a body at a specific ratio is effective and completed the present invention.

In the curable hard coat agent composition of the present invention, the cured film has excellent hardness and scratch resistance, and further has small curl and excellent flex resistance.

The present invention relates to a curable hard coat agent composition comprising the following (meth) acrylate mixture.
(Meth) acrylate mixture: pentaerythritol tri (meth) acrylate (hereinafter referred to as “tri-form”), pentaerythritol tetra (meth) acrylate (hereinafter referred to as “tetra-form”) and An area ratio of a compound (hereinafter referred to as “compound M”) obtained by Michael addition to a (meth) acryloyl group was measured by liquid chromatography under the following conditions. Containing mixture.
Tri-form: Tetra-form: Compound M = 0.1-2.0: 100: 15.0-50.0
Liquid chromatography measurement condition equipment: high-performance liquid chromatograph (HPLC), detector: ultraviolet detector, column type: column consisting of silica gel (particle diameter: 1.7 μm) modified with an alkyl group having 18 carbon atoms (particle diameter: 1.7 μm) ID: 2.1 mm × length: 150 mm), column temperature: 40 ° C., eluent: 0.03% by weight trifluoroacetic acid aqueous solution / acetonitrile = 60/40 (initial) → 50/50 (10 minutes) → 30 / 70 (15 minutes) → 0/100 (18-20 minutes)
Hereinafter, the present invention will be described in detail.

1. (Meth) acrylate mixture The (meth) acrylate mixture, which is an essential component of the composition of the present invention, is an area ratio of a tri-form, a tetra-form and a compound M measured by liquid chromatography under the above-mentioned conditions. When the area is 100, the mixture is contained in the following area ratio.
Tri-form: Tetra-form: Compound M = 0.1-2.0: 100: 15.0-50.0

  Compound M is a compound represented by the following formula (1). In the formula (1), R represents a hydrogen atom or a methyl group.

The measurement conditions for liquid chromatography in the present invention are as described above.
Silica gel modified with an alkyl group having 18 carbon atoms is commercially available, such as Acquity BEH C18 manufactured by Nippon Waters Co., Ltd.
Moreover, it is preferable to measure as the following conditions.
Flow rate: 0.3 mL / min, UV detector detection wavelength: 210 nm, sample concentration: 0.1 wt% acetonitrile solution, injection volume: 2 μL
In the present invention, the area value of the tetra-body peak is defined as 100, and the relative area value of the tri-body and the peak of the compound M is calculated.

In the present invention, in the (meth) acrylate mixture, the area ratio of the tri isomer, the tetra isomer and the compound M is set to the tri isomer: tetra isomer: compound M = 0.1 to 2.0: 100: 15.0 to 50.0. And Thereby, the curing rate is excellent, the volume shrinkage at the time of curing is reduced, the cured film is excellent in physical properties such as hardness, and the emulsification resistance is excellent.
In particular, by setting the ratio of the tri- and tetra-isomers within the above range, the emulsion can be excellent in anti-emulsification properties, and by setting the ratio of the compound M within the above range, the curability is excellent and during curing. The volume shrinkage can be reduced.

1) Manufacturing method of (meth) acrylate mixture The (meth) acrylate mixture is arbitrary as long as it contains a tri-form, a tetra-form and a compound M in the above proportions, and can also be produced by blending each component. However, those obtained by heating and stirring the tri- and tetra-isomers in the presence of an acid catalyst are simple and preferred.
Below, the said manufacturing method is demonstrated in detail.

1-1) Raw material (meth) acrylate In this production method, a tri-form and a tetra-form are used as a raw material.
The ratio of the tri- and tetra-isomers of the raw material is preferably tri-isomer: tetra-isomer = 50.0 to 200.0: 100 in an area ratio measured by liquid chromatography under the conditions described later.
It is preferable that the tri- and tetra-forms of the raw material are easily obtained and use an esterification reaction product of pentaerythritol and (meth) acrylic acid. In this case, what contains 50 to 80 weight% of a tri body and a tetra body in an esterification reaction material is preferable. In this case, compounds other than tri- and tetra-forms may be included. Specific examples include unreacted pentaerythritol, unreacted (meth) acrylic acid, mono (meth) acrylate, pentaerythritol di (meth) acrylate, and other (meth) acrylate oligomers.
Furthermore, (meth) acrylates other than these may be included. Specific examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

1-2) Acid-catalyzed acid catalyst is used for the addition reaction of a tri-form hydroxyl group to a tetra-form (meth) acryloyl group. This reaction is usually referred to as a Michael addition reaction.
Various acid catalysts can be used. Specifically, sulfuric acid, methanesulfonic acid, paratoluenesulfonic acid, tungstophosphoric acid, tungstosilicic acid, molybdophosphoric acid, molybdosilicic acid, boron trifluoride etherate, tin tetrachloride, etc. Can be mentioned. Among these, methanesulfonic acid and paratoluenesulfonic acid are preferable because they have high catalytic activity, do not deactivate even in the presence of water, and have few side reactions.

  As the usage amount of the acid catalyst, the total amount of the tri-form, tetra-form and other (meth) acrylates in the case where (meth) acrylate other than the tri-form and tetra-form is included relative to the total quantity of the tri-form and tetra-form The amount is preferably 0.1 to 15% by weight, more preferably 1.0 to 10% by weight based on the amount [hereinafter referred to as the total amount of (meth) acrylate]. By making the content 0.1% by weight or more, the addition reaction can be sufficiently progressed. By making the content 15% by weight or less, the reaction system due to excessive heat generation can be prevented from becoming unstable, and the product can be colored. Furthermore, gelation can be prevented.

1-3) In the production method of other component (meth) acrylate mixtures, it is preferable to use a reaction solvent as necessary.
The reaction solvent is used for diluting the above essential components, for example, aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, and methyl ethyl ketone and cyclohexanone. Examples include ketones.
As the reaction solvent, considering the solubility of the substrate, one kind may be used alone, or two or more kinds may be used in arbitrary combination.
When a reaction solvent is used, the mixing ratio may be selected according to the purpose, but a ratio in which the solid content of the reaction solution is usually 10 to 80% by weight is preferable.

In the method for producing a (meth) acrylate mixture, a polymerization inhibitor for suppressing radical polymerization of the (meth) acryloyl group may be added to the reaction solution, or an oxygen-containing gas may be introduced into the reaction solution. preferable.
Examples of the polymerization inhibitor include hydroquinone, tert-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, benzoquinone, phenothiazine and the like. Organic polymerization inhibitors, inorganic polymerization inhibitors such as copper chloride and copper sulfate, and organic salt polymerization inhibitors such as copper dibutyldithiocarbamate. A polymerization inhibitor may be used individually by 1 type, or may be used in combination of 2 or more types arbitrarily.
As a ratio of a polymerization inhibitor, 50-20,000 ppm is preferable with respect to the total amount of the tri body and tetra body of a raw material, or the (meth) acrylate total amount. By setting the proportion of the polymerization inhibitor to 50 ppm or more, the effect of preventing polymerization can be made sufficient, while by setting it to 20,000 ppm or less, the curability of the product is prevented from being lowered, and the product is colored. Can be prevented.
Examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like.

1-4) Production conditions A preferred production method of the (meth) acrylate mixture is a method of heating and stirring the tri- and tetra-isomers in the presence of an acid catalyst.
The reaction may be performed by heating and stirring the tri-form and tetra-form in the reaction solvent as necessary in the presence of the acid catalyst and, if necessary, the polymerization inhibitor.

  In this case, the reaction temperature is preferably 60 to 130 ° C. When the reaction temperature is less than 60 ° C., the reaction is slow, and when it exceeds 130 ° C., the reaction system may become unstable or gel.

  The reaction time may be appropriately set according to the ratio of the raw tri- and tetra-forms, the reaction conditions, the ratio of the finally obtained tri- and tetra-forms, etc., but preferably 2 to 20 hours.

Since the reaction may deteriorate in the presence of moisture, the tri- and tetra-forms obtained by the esterification reaction described below should be carried out under reduced pressure when used without drying. Is preferred.
The degree of reduced pressure may be appropriately set according to the purpose, but is preferably 45 to 95 kPa, and more preferably 50 to 90 kPa.

An example of a preferred production method is that a reactor equipped with a stirrer and a thermometer is charged with a predetermined amount of tri- and tetra-isomers, and if necessary, a reaction solvent is used, and an appropriate amount of an acid catalyst and further a polymerization inhibitor are charged. A method of heating and stirring for a predetermined time under stirring can be mentioned.
After completion of the reaction, the reaction solution is neutralized and washed with water, and the aqueous layer is separated. Then, the organic layer is heated under reduced pressure to distill off the solvent to obtain the desired (meth) acrylate mixture.

2) Manufacturing method of (meth) acrylate mixture using esterification reaction product As a manufacturing method of (meth) acrylate mixture, it is also possible to manufacture by using an esterification reaction product of pentaerythritol and (meth) acrylic acid as it is. (Hereinafter referred to as the second manufacturing method).
That is, pentaerythritol and (meth) acrylic acid are heated and stirred in the presence of an acid catalyst to obtain a mixture of a tri isomer and a tetra isomer, and then the mixture is heated and stirred in the presence of an acid catalyst (meta ) An acrylate mixture may be produced.

  As a method for the dehydration esterification reaction of pentaerythritol and (meth) acrylic acid, various conventionally known methods may be used. For example, polyhydric alcohol and (meth) acrylic acid are heated and stirred in the presence of an acid catalyst. The method of dehydrating is mentioned.

  In the second production method, the raw material pentaerythritol may contain other polyhydric alcohol as necessary. Specific examples include dipentaerythritol. In this case, the other polyhydric alcohol is preferably 40% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less with respect to the total amount of the raw material alcohol.

  The proportion of pentaerythritol and (meth) acrylic acid used may be appropriately determined so that the tri- and tetra-isomers in the esterification reaction product are within the above preferred range, but with respect to 1 mol of hydroxyl group in pentaerythritol. The molar ratio of (meth) acrylic acid is preferably 0.6 to 1.8. By controlling this ratio to 0.6 or more, the addition reaction between a tetra-form and a compound having a hydroxyl group other than a tri-form, for example, unreacted pentaerythritol or (meth) acrylate having 2 or more hydroxyl groups, can be suppressed. It is possible to prevent thickening of the product and difficulty in separating the two layers in the water washing after the reaction. On the other hand, by setting it to 1.8 or less, unreacted (meth) acrylic acid is reduced, which is economical, and the amount of alkali in neutralization can also be reduced.

  The most suitable ratio of pentaerythritol and (meth) acrylic acid varies depending on the ratio of the desired tri- and tetra-isomers and reaction conditions, but can be easily set by an experimental method. Moreover, in order to control the ratio of the tri isomer and the tetra isomer in the esterification reaction product to the target ratio, it is preferable to measure the amount of water distilled by the reaction.

As the acid catalyst, the same ones as described above can be used.
The use ratio of the acid catalyst is preferably 0.1 to 15% by weight, more preferably 1.0 to 10% by weight, based on the total amount of pentaerythritol and (meth) acrylic acid.

  As reaction temperature, 80-130 degreeC is preferable. By setting the reaction temperature to 80 ° C. or higher, the reaction rate can be increased. On the other hand, by setting the reaction temperature to 130 ° C. or lower, the reaction system becomes stable and gelation can be prevented.

  What is necessary is just to set reaction time suitably according to the kind of raw material to be used, a ratio and quantity, the ratio of the tri body and tetra body finally obtained, etc., However, 4 to 40 hours are preferable.

The reaction is preferably carried out under reduced pressure. Thereby, dehydration can be performed efficiently, the reaction can be completed in a short time, and coloring of the resulting composition can be prevented.
The degree of reduced pressure may be appropriately set according to the purpose, but is preferably 45 to 95 kPa, and more preferably 50 to 90 kPa.

In the esterification reaction, it is preferable to use a reaction solvent because dehydration can be performed efficiently. As the reaction solvent, the same solvents as described above can be used.
Moreover, in the manufacturing method of this invention, it is preferable to add the polymerization inhibitor for suppressing that a (meth) acryloyl group carries out radical polymerization to a reaction liquid, or introduce | transduces oxygen-containing gas into a reaction liquid. Examples of the polymerization initiator and oxygen-containing gas include the same ones as described above.

In the second production method, the (meth) acrylate mixture is produced by heating and stirring the mixture of the tri-form and the tetra-form obtained by the esterification reaction in the presence of an acid catalyst.
In this case, without adding an acid catalyst to the resulting mixture of tri- and tetra-isomers, it may be heated as it is in the presence of the acid catalyst used in the esterification reaction, or a new acid catalyst is added. And may be heated.
There is also a method in which the obtained reaction mixture is neutralized and washed with water, the organic layer is separated, and an acid catalyst is newly added to the obtained organic layer and heated.
In this case, examples of the alkali for neutralization include an aqueous sodium hydroxide solution. According to the neutralization / water washing treatment, water-soluble components such as unreacted (meth) acrylic acid in the reaction mixture can be removed. Thereby, it is possible to preferably control the ratio of the tri-form and the tetra-form to be generated to the target ratio, and to prevent the separation of the water layer and the organic layer in the water washing step after the addition reaction. Can do.

  According to the second production method, since the (meth) acrylate mixture can be produced in one pot using pentaerythritol and (meth) acrylic acid as raw materials, the process becomes simple and the cost is low.

2. Curable hard coat agent composition present invention is a curable hard coat agent composition containing the (meth) acrylate mixture.
Various components described in detail below can be blended in the composition.

1) The ethylenically unsaturated compound other than the (meth) acrylate [hereinafter referred to as “other unsaturated compound”] can be blended with the other ethylenically unsaturated compound composition.

  Examples of other unsaturated compounds include one compound having ethylenic unsaturation and two or more (meth) acryloyl group compounds (hereinafter referred to as poly (meth) acrylate).

Examples of the compound having one ethylenic unsaturation include a vinyl compound and a compound having one (meth) acryloyl group (hereinafter referred to as mono (meth) acrylate).
Examples of the vinyl compound include N-vinylpyrrolidone, N-vinylcaprolactam and (meth) acrylamide.
Examples of mono (meth) acrylates include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate; perfluorooctylethyl (meth) acrylate, and the like Perfluoroalkyl (meth) acrylates; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 1,4-butanediol mono (meth) acrylate; phosphoric acid ( Examples include (meth) acrylates having a phosphate group such as (meth) acrylate and ethylene oxide-modified phosphoric acid (meth) acrylate; and alicyclic mono (meth) acrylates such as isobornyl acrylate. In addition to these, tetrahydrofurfuryl (meth) acrylate, carbitol (meth) acrylate, (meth) acryloylmorpholine, maleimide (meth) acrylate, glycidyl (meth) acrylate, and the like can be given.
(Meth) acrylamides include (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and N-methylol (meth). Examples include acrylamide.

Examples of poly (meth) acrylates include (meth) acrylates having two (meth) acryloyl groups such as pentaerythritol di (meth) acrylate monostearate; pentaerythritol tri (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate having three (meth) acryloyl groups such as (meth) acrylate; and di (2- (meth) acryloyloxyethyl) isocyanurate, tris (2- (meth) acryloyloxyethyl) isocyanurate Di or tri (2- (meth) acryloyloxyalkyl) isocyanurate such as di (2- (meth) acryloyloxypropyl) isocyanurate and tris (2- (meth) acryloyloxypropyl) isocyanurate And di (2- (meth) acryloyl Xylethyl) cyanurate, tris (2- (meth) acryloyloxyethyl) cyanurate, di (2- (meth) acryloyloxypropyl) cyanurate and tris (2- (meth) acryloyloxypropyl) cyanurate And di (2- (meth) acryloyloxyalkyl) cyanurate, etc.
In addition to these, it has four or more (meth) acryloyl groups such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di (trimethylolpropane) tetra (meth) acrylate, etc. (meth) Acrylates can also be used.

  In addition, oligomers such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate can also be used.

  Examples of the urethane (meth) acrylate oligomer include a reaction product obtained by further reacting a hydroxyl group-containing (meth) acrylate with a polyol and an organic polyisocyanate reaction product. Here, examples of the polyol include a low molecular weight polyol, polyethylene glycol, and polyester polyol, and examples of the low molecular weight polyol include ethylene glycol, propylene glycol, cyclohexanedimethanol, and 3-methyl-1,5-pentanediol. Examples of the polyether polyol include polyethylene glycol and polypropylene glycol. Examples of the polyester polyol include these low molecular weight polyols and / or polyether polyols, adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid. And a reaction product with an acid component such as a dibasic acid or an anhydride thereof. Examples of the organic polyisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

  As a polyester (meth) acrylate oligomer, the dehydration condensate of a polyester polyol and (meth) acrylic acid is mentioned. Examples of the polyester polyol include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, and these And a reaction product from a polyol such as an alkylene oxide adduct and an acid component such as a dipic acid such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or an anhydride thereof.

  Epoxy acrylate is obtained by addition reaction of unsaturated carboxylic acid such as (meth) acrylic acid to epoxy resin. Epoxy (meth) acrylate of bisphenol A type epoxy resin, epoxy (meth) of phenol or cresol novolac type epoxy resin Examples thereof include (meth) acrylic acid addition reactants of acrylate and polyether diglycidyl ether.

Other unsaturated compounds can be appropriately selected according to the use and purpose of the composition.
For the purpose of further imparting hardness to the cured film of the composition, it is preferable to blend the poly (meth) acrylate described above.
For the purpose of further imparting abrasion resistance, toughness and the like to the cured film of the composition, it is preferable to blend the aforementioned urethane (meth) acrylate oligomer.
When the composition of the present invention is used for outdoor use, etc., for the purpose of imparting weather resistance to the cured film, di- or tri (2- (meth) acryloyloxyalkyl) isocyanurate or / And di- or tri (2- (meth) acryloyloxyalkyl) cyanurate are preferably blended.

  The blending ratio of the other unsaturated compound may be appropriately set according to the use and purpose of the composition, but is 5 to 90 based on the total weight of the ethylenically unsaturated compound contained in the composition of the present invention. % By weight is preferred, more preferably 7 to 70% by weight.

2) When using a polymerization initiator composition as an active energy ray curable composition, especially when setting it as a visible light or an ultraviolet curable composition, a photoinitiator is mix | blended with a composition. In addition, when setting it as an electron beam curable composition, it is not necessary to mix | blend a photoinitiator.

Specific examples of the photopolymerization initiator include benzoin such as benzoin, benzoin methyl ether and benzoin propyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1 Acetophenones such as dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N, N-dimethylaminoacetophenone; 2-methyl Anthraquinones such as anthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthate Such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide, etc. And 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.
These photopolymerization initiators may be used alone or in combination of two or more.

A photosensitizer can be used in combination with the photopolymerization initiator as necessary. Examples of photosensitizers include dye sensitizers such as xanthene, thioxanthene, coumarin, and thiocoumarin; ureas such as o-tolylthiourea; sulfur such as sodium diethyldithiophosphate and s-benzylisothiouronium-p-toluenesulfonate. Compounds: N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethylamine, triethanolamine and the like.
These photosensitizers may be used alone or in combination of two or more.

  When mix | blending a photoinitiator, with respect to 100 weight part of (meth) acrylate mixtures, or when mix | blending another unsaturated compound, 0.01-20 weight with respect to 100 weight part of these total amounts. Parts, preferably 0.1 to 10 parts by weight.

When the composition is used as a thermosetting composition, a thermal polymerization initiator is added to the composition.
A well-known thing can be used as a thermal-polymerization initiator.

3) Organic solvent The composition of the present invention can be used in a solvent-free form, but an organic solvent may be blended as necessary according to the substrate to be applied, the coating method, the target viscosity, and the like. it can.
Organic solvents include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane and mineral spirits; halogenated hydrocarbons such as ethylene chloride and methylene chloride; methanol, ethanol and isopropyl alcohol Alcohol; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether and diethylene glycol diethyl ether and other ethers; ethyl acetate, butyl acetate, ethyl propionate and ethyl cellosolve acetate, methyl ethyl ketone, Ketones such as methyl isobutyl ketone and cyclohexanone; and methyl cellosolve, Cellosolves such as Ruserosorubu and butyl cellosolve and the like.
An organic solvent may be used independently or may use 2 or more types together.
A preferable blending ratio of the organic solvent may be appropriately set according to the target viscosity and the like, but it is preferably blended at a ratio of 10 to 90% by weight as a solid content, more preferably 20 to 80% by weight. is there.

4) Polymer The composition of the present invention can be blended with a polymer for the purpose of relieving stress during curing and preventing the occurrence of curing shrinkage and curling. In particular, it is preferable when used for a display body (liquid crystal display, plasma display, touch panel, etc.) provided with a film having a hard coat layer as a protective layer on the surface.
As the polymer, various polymers can be used as long as the stress at the time of curing can be relieved, and examples thereof include (meth) acrylate polymers and organopolysiloxanes, and (meth) acrylate polymers are preferred.

4-1) (Meth) acrylate polymer A (meth) acrylate polymer essentially comprises an alkyl (meth) acrylate, and if necessary, a radical polymerizable monomer (hereinafter referred to as a copolymer) that can be copolymerized with these (meth) acrylates. And a polymer obtained by copolymerizing a polymerizable monomer).
Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
The weight average molecular weight of the (meth) acrylate polymer is preferably 1,000 to 500,000, more preferably 5,000 to 200,000, and still more preferably 8,000 to 100,000. When the weight average molecular weight is 1,000 or more, the effect of reducing curing shrinkage is large, and when it is 500,000 or less, the hardness is sufficiently high.
Here, the weight average molecular weight means a value obtained by converting the molecular weight measured by gel permeation chromatography (GPC) into polystyrene.

  As the (meth) acrylate polymer, by selecting a copolymerizable monomer according to the purpose, various performances can be imparted to the cured film in addition to the stress relaxation performance at the time of curing the composition.

A) In the case of imparting antistatic performance or the like to the cured film of the composition such as antistatic performance, it has a vinyl group-containing monomer having a quaternary ammonium base or / and a phosphate group as a copolymerizable monomer. It is preferable to use a vinyl group-containing monomer.

Examples of the vinyl group-containing monomer having a quaternary ammonium base include compounds having a quaternary ammonium group such as a trialkylammonium group and a vinyl group.
Specifically, aminoalkyl groups containing 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate and the like ( (Meth) acrylic acid esters; 2- (dimethylaminoethoxy) ethyl (meth) acrylate, 2- (diethylaminoethoxy) ethyl (meth) acrylate, 3- (dimethylaminoethoxy) propyl (meth) acrylate and other aminoalkoxyalkyl groups Containing (meth) acrylic acid esters; N- (2-dimethylaminoethyl) (meth) acrylamide, N- (2-diethylaminoethyl) (meth) acrylamide, N- (2-dimethylaminopropyl) (meth) acrylamide, N- ( -(Meth) acrylic monomers such as N-aminoalkyl group-containing (meth) acrylamides such as (dimethylaminopropyl) (meth) acrylamide are quaternized with methylene chloride, dimethyl sulfate, diethyl sulfate, dimethyl carbonate, diethyl carbonate, etc. It is obtained as a modified quaternary salt.

More specific examples include 2-hydroxy-3- (meth) acryloxypropyltrimethylammonium chloride, 2-hydroxy-3- (meth) acryloxypropyltriethylammonium bromide, 2-hydroxy-3- (meth) acrylic. Oxypropyltributylammonium chloride, 2-hydroxy-3- (meth) acryloxypropylmethylethylbutylammonium chloride, 2-hydroxy-3- (meth) acryloxypropyldimethylphenylammonium chloride, 2-hydroxy-3-methacryloxy Examples thereof include propyldimethylcyclohexyl ammonium chloride.
These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the vinyl group-containing monomer having a phosphoric acid group include a (meth) acrylate having a phosphoric acid group, and specifically, phosphoric acid (meth) acrylate and ethylene oxide-modified phosphoric acid (meth) acrylate. It is done.

B) In the case where it is desired to further impart scratch resistance or the like to the cured film of the composition such as scratch resistance, a vinyl group-containing monomer having a polydialkylsiloxane group and / or a fluorinated alkyl group is used as a copolymerizable monomer. It is preferable to use a vinyl group-containing monomer.
In the vinyl group-containing monomer having a polydialkylsiloxane group, the polydialkylsiloxane group is preferably a polydimethylsiloxane group. The vinyl group-containing monomer having a polydialkylsiloxane group is preferably a (meth) acrylate having a polydimethylsiloxane group. Specific examples of the (meth) acrylate having a polydimethylsiloxane group include (meth) acryloxypropyl polydimethylsiloxane, (meth) acryloxybutyl polydimethylsiloxane, (meth) acryloxypropyl polymethylphenylsiloxane, and the like.
Examples of the vinyl group-containing monomer having a fluorinated alkyl group include (meth) acrylate having an alkyl group in which a hydrogen atom is substituted with a fluorine atom. Specific examples of the (meth) acrylate include perfluorooctylethyl (meth) acrylate, perfluorohexylethyl (meth) acrylate, N-methylperfluorooctylsulfonamidoethyl (meth) acrylate, and N-methylperfluorohexylsulfone. Examples include amidoethyl (meth) acrylate, N-propylperfluorohexylsulfonamidoethyl (meth) acrylate, N-propylperfluorooctylsulfonamidoethyl (meth) acrylate, and perfluoroheptylcarbonamidoethyl (meth) acrylate.
Among these, perfluorooctylethyl (meth) acrylate in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is preferable.

C) A (meth) acrylate polymer having an ethylenically unsaturated group as a (meth) acrylate polymer when it is desired to further impart solvent resistance and abrasion resistance to the cured film of the unsaturated acrylic polymer composition. It is preferable to use [hereinafter referred to as “unsaturated acrylic polymer”].

  The unsaturated acrylic polymer has a (meth) acrylate polymer having a reactive functional group in the side chain (hereinafter referred to as “reactive acrylic polymer”) and a group capable of reacting with the reactive functional group. It can be obtained by reacting an ethylenically unsaturated compound (hereinafter referred to as “reactive unsaturated compound”).

As the reactive functional group of the (meth) acrylate polymer having a reactive functional group in the side chain, a hydroxyl group, a carboxyl group, an epoxy group, and the like are preferable.
As the functional group of the ethylenically unsaturated compound having a group capable of reacting with these reactive functional groups, an isocyanate group, a carboxyl group, an acid halide group, a hydroxyl group, an epoxy group, and the like are preferable.

  The method for producing an unsaturated acrylic polymer by reacting a reactive acrylic polymer with a reactive unsaturated compound is not particularly limited and can be produced by a conventionally known method. Examples of the acrylic polymer and the reactive unsaturated compound include a method of selecting the following (1) to (3).

(1) Reactive acrylic polymer: (meth) acrylate polymer having a hydroxyl group Reactive unsaturated compound: (meth) acryloylethylisocyanate, isocyanate group-containing urethane (meth) acrylate, (meth) acrylic acid and (meth) Acrylic acid chloride, etc.

(2) Reactive acrylic polymer: (meth) acrylate polymer having carboxyl group Reactive unsaturated compound: Compound containing hydroxyl group and (meth) acryloyl group, or Compound having epoxy group and (meth) acryloyl group

(3) Reactive acrylic polymer: (meth) acrylate polymer having an epoxy group Reactive unsaturated compound: (meth) acrylic acid, (meth) acrylic acid dimer, ω-carboxy-polycaprolactone mono (meth) acrylate And compounds having a carboxyl group and a (meth) acryloyl group, such as monohydroxyethyl (meth) acrylate phthalate

The method for producing an unsaturated acrylic polymer will be described by taking (3) as an example.
First, a (meth) acrylate polymer having an epoxy group is produced as a reactive acrylic polymer. The said polymer is manufactured by homopolymerizing the (meth) acrylate which has an epoxy group, or copolymerizing with a monomer other than this.
Examples of the (meth) acrylate having an epoxy group include glycidyl (meth) acrylate and (meth) acrylate having an alicyclic epoxy group (for example, “CYCLOMER M100” and “CYCLOMER a200” manufactured by Daicel Chemical Industries, Ltd.). 4-hydroxybutyl acrylate glycidyl ether and the like.
As the monomer for copolymerization, unsaturated monomers having no carboxyl group such as (meth) acrylic acid ester, styrene, vinyl acetate and acrylonitrile are preferable.
Next, an unsaturated acrylic polymer can be obtained by addition-reacting a compound having a carboxyl group and a (meth) acryloyl group to the epoxy group of the (meth) acrylate polymer having an epoxy group.

  The weight average molecular weight of the unsaturated acrylic polymer is preferably 2,000 to 80,000, more preferably 5,000 to 50,000, and still more preferably 8,000 to 35,000. When the weight average molecular weight is 5,000 or more, the effect of reducing curing shrinkage is large, and when it is 80,000 or less, the hardness is sufficiently high.

In the case of imparting antifouling property or the like to the cured film as an unsaturated acrylic polymer, a polysiloxane block copolymer unit can be introduced.
Specifically, in the production of a reactive acrylic polymer, polymerization is performed using the above-described monomer in the presence of polysiloxane having an azo group, and this is reacted with a reactive unsaturated compound, etc. Is mentioned. For the selection of the polysiloxane or monomer having an azo group, the same photoreactive silicone acrylic copolymer as described in JP-A-2008-056789 can be used.

  The (meth) acryloyl group equivalent of the unsaturated acrylic polymer is preferably 100 to 400 g / eq, and more preferably 200 to 300 g / eq. When the (meth) acryloyl group equivalent of the polymer (B) is within this range, curing shrinkage can be reduced and the hardness can be sufficiently increased.

  The blending ratio of the unsaturated acrylic polymer is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, and further preferably 15 to 50% by weight based on 100 parts by weight of the total solid content in the composition. preferable. By setting the blending ratio of the unsaturated acrylic polymer within this range, a cured film having a sufficiently high hardness can be obtained and curing shrinkage can be reduced, so that the curl of the film having the cured film can also be reduced. .

4-2) Organopolysiloxane The organopolysiloxane may be any of various compounds that have been known as silicone oils, silicone rubbers, etc., and have a structure in which the Si—O—Si bond is the main skeleton and is substituted with an organic group. Compounds can be used.
The weight average molecular weight of the organopolysiloxane is preferably 500 to 100,000, more preferably 1,000 to 50,000. When the weight average molecular weight is 500 or more, the effect of reducing curing shrinkage is large, and when it is 100,000 or less, the hardness is sufficiently high.

  As an organopolysiloxane, an organopolysiloxane having an ethylenically unsaturated group (hereinafter referred to as “unsaturated organopolysiloxane”) is used to further impart solvent resistance and abrasion resistance to the cured film of the composition. It is preferable to use it.

Specific examples of the unsaturated organopolysiloxane include a copolymer of an alkoxysilane and a radically polymerizable unsaturated group-containing alkoxysilane.
Alkoxysilanes include tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltri Examples include ethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.
Examples of the radical polymerizable unsaturated group-containing alkoxysilane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3 -Acryloxypropyltrimethoxysilane and the like.
The unsaturated organopolysiloxane can be produced by mixing and heating an alkoxysilane and a radically polymerizable unsaturated group-containing alkoxysilane according to a conventional method to advance polycondensation.

  In addition, for the purpose of improving the solubility in the composition, an ether-modified organopolysiloxane can be used. Examples of the organopolysiloxane include compounds described in JP-A-2007-231138.

5) Weather resistance improver When the composition of the present invention is used outdoors, it is preferable to add a weather resistance improver for the purpose of imparting weather resistance to the cured film.
Examples of the weather resistance improver include ultraviolet absorbers, light stabilizers and antioxidants.

5-1) Ultraviolet absorbers Examples of the ultraviolet absorber include benzophenone, benzotriazole, phenyl salicylate, and phenyl benzoate compounds.
Among these, ultraviolet absorbers having a maximum absorption wavelength in the range of 240 to 380 nm are preferable. In particular, benzophenone-based ultraviolet absorbers are also polycarbonates because they can be contained in a large amount in the composition. From the viewpoint that yellowing of the base material such as benzotriazole can be prevented, a benzotriazole-based ultraviolet absorber is preferable.
Specific examples of the ultraviolet absorber include the following compounds.
Examples of the benzophenone ultraviolet absorber include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 4- Examples include dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,2′-dihydroxy-4,4′-dimethoxybenzophenone.
Examples of the phenyl salicylate UV absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p- (1,1,3,3-tetramethylbutyl) phenyl salicylate, and 3-hydroxyphenylbenzoate. And phenylene-1,3-dibenzoate.
Examples of benzotriazole ultraviolet absorbers include 2- (2-hydroxy-5′-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -5-chlorobenzotriazole. 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4- Octylphenyl) benzotriazole and the like.

5-2) Light stabilizer Examples of the light stabilizer include hindered amine and benzoate light stabilizers.
Examples of hindered amine light stabilizers include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate. 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), dimethyl succinate -1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 1- [2- [3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, (mixed , 2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethyl-4- Piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butane Examples thereof include tetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate.
Examples of the benzoate-based light stabilizer include 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

5-3) Antioxidants As antioxidants , triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxylphenyl) propionate] and 1,6-hexanediol-bis [3 , 5-di-t-butyl-4-hydroxyphenyl) propionate] and the like.

The weather resistance improver may be used alone or in combination of two or more.
A preferable blending ratio of the weather resistance improver is 0.01 to 5 parts by weight with respect to 100 parts by weight of the composition. If this proportion is less than 0.01 parts by weight, the effect of blending a weather resistance improver cannot be obtained. On the other hand, if it exceeds 5 parts by weight, the curability of the composition is lowered or the resulting composition The wear resistance of the cured film may be reduced.

6) Inorganic fine particles Inorganic fine particles are preferably blended for the purpose of imparting scratch resistance and impact resistance to the cured film.
Examples of the inorganic fine particles include carbon black such as channel black, furnace black, thermal black and acetylene black; silica such as finely divided silicic acid, hydrous silicic acid, diatomaceous earth and colloidal silica; finely divided magnesium silicate, talc, soapstone, Silicates such as stearite, calcium silicate, magnesium aluminosilicate and sodium aluminosilicate; sedimentation (active, dry, heavy or light) carbonates such as calcium carbonate, chalk and magnesium carbonate; kaolin clay, sericite Clay, vilophyllite clay, montmorillonite clay, bentonite and acid clay etc .; alumina (hydrate) such as aluminum oxide, aluminum hydroxide and alumina white; zirconia such as zirconium oxide; And aluminum sulfate, such as satin white; barytes, barium sulfate, such as precipitated barium sulfate, and lithopone; gypsum such as anhydrous and hemihydrate gypsum and the like. Also included are white lead, mica, zinc white, titanium oxide, activated calcium fluoride, zeolite, cement, lime, calcium sulfite, molybdenum disulfide, asbestos, glass fiber, lock fiber, microballoon (shirasu, glass) and the like. .
As the particle diameter of the inorganic fine particles, the volume average particle diameter is preferably 0.01 to 5 μm.
Two or more kinds of these inorganic fine particles may be used in combination.

When blending inorganic fine particles into the composition, it is preferable to blend a leveling agent for the purpose of improving the dispersibility of the inorganic fine particles.
As the leveling agent, in addition to those described later, fluorine-based surfactants described in JP-A-2007-262287 can also be used.

7) Other components In addition to the above-mentioned components, a pigment, a dye, an antifoaming agent, an organic filler, a dispersant, a thickener (thixotropic agent), a leveling agent, a polymerization inhibitor, and the like are added as necessary. You can also.
Examples of the leveling material include silicon-based surfactants and fluorine-based surfactants.
Further, silane compounds such as tetramethoxysilane and tetraethoxysilane, and condensates of silane compounds can also be blended.
In addition, when imparting an antistatic function to the cured film, an antistatic agent such as a quaternary ammonium salt compound, antimony-doped tin oxide, zinc antimonate, tin-doped indium oxide, or phosphorus-doped tin oxide should be blended. You can also.

3. Usage and application
1) General As a method for using the composition of the present invention, a conventional method may be used.
Specific examples include a method in which the composition of the present invention is applied to a substrate and cured by irradiation with active energy rays or heating.

Examples of the base material include various base materials to which a covering material is usually applied. Specifically, plastic, metal, glass, concrete, wood such as natural wood and synthetic wood, stone, paper and the like can be mentioned.
The composition of the present invention can be preferably used especially for surface protection of plastics, that is, for hard coat applications.

Specific examples of plastics include polymethyl methacrylate, polycarbonate, polyester, poly (polyester) carbonate, polystyrene, polyvinyl chloride, ABS resin, AS resin, polyamide, polyarylate, polymethacrylimide, polyallyldi Examples include glycol carbonate.
Among these, polymethyltyl methacrylic resin, polycarbonate, polystyrene, and polymethacrylimide are particularly effective to apply the composition of the present invention because they are excellent in transparency and have a strong demand for improving wear resistance.
The plastic form can be preferably applied to a molded product, and there are a sheet-shaped molded product, a film-shaped molded product, various injection molded products, and the like made of these plastics.

The coating method may be in accordance with a conventional method. Specifically, when the film thickness is thin, brush coating, dip coating, roll coating, spray coating, spin coating, and the like can be given.
The film thickness may be appropriately set depending on the purpose and application, but is preferably 0.1 to 30 μm.

As a curing means such as an active energy ray irradiation method and a heating method, a general method known as a curing method for a radical polymerizable compound may be employed.
In the case of curing by irradiation with active energy rays, visible rays, ultraviolet rays, electron beams and the like can be used as the active energy rays, and ultraviolet rays are preferred because the apparatus that can be used is simple.
In the case of curing by heating, examples of the heating device include a steam heater, an electric heater, an infrared heater, and a far infrared heater. What is necessary is just to set suitably as a heating temperature according to the composition to be used and the objective, and 30-100 degreeC is preferable.

  More specific applications to which the covering material can be applied include paints such as woodwork, topcoat paints such as mortar and slate, and waterproof paints for printed circuit boards constituting electronic circuits.

The composition of the present invention can be suitably used particularly as a hard coat agent.
Specific use forms of hard coating agents; coating of optical lenses such as glasses lenses, contact lenses, Fresnel lenses and lenticular lenses; coating of optical disks such as CD and DVD; coating of mobile phone bodies; liquid crystal display, plasma Examples include surface coating of screen panels and protective films of display materials such as displays, organic EL and touch panels; coating of automobile headlights and glass substitute plastics; and coating of home appliances.
The composition of the present invention is excellent in the curing rate, reduced in volume shrinkage at the time of curing, and the cured film is also excellent in physical properties such as hardness, so that it can be suitably used for the above applications.
The composition of the present invention can be more preferably used as an active energy ray-curable hard coat agent. The usage method in this case is demonstrated below.

2) Hard coat for film The use of the composition of the present invention for a hard coat on the surface of a film in, for example, a display body (liquid crystal display, plasma display, touch panel, etc.) provided with a film on the surface will be described.

Examples of film substrates include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films such as polypropylene, polyethylene, and polymethylpentene-1; cellulose-based films such as triacetyl cellulose; polystyrene films, polyamides Film, polycarbonate film, norbornene resin film (for example, “ZEONOR” manufactured by Nippon Zeon Co., Ltd.), modified norbornene resin film (for example (“ARTON” manufactured by JSR Corporation)), cyclic olefin copolymer film (for example, Mitsui) “Apel” manufactured by Kagaku Co., Ltd.), etc. Two or more of these films may be bonded together.
These films may be in sheet form. As for the thickness of a film base material, 20-500 micrometers is preferable. The film to be used may be one provided with a handle or an easy adhesion layer.

As a method of applying to the film substrate, for example, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, dip coating, spinner coating, wheeler coating, brush coating, solid coating by silk screen, A wire bar coat, a flow coat, etc. are mentioned. Also, printing methods such as offset printing and letterpress printing may be used.
Among these, gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating, and flow coating are preferable because a coating film having a more constant thickness can be obtained.

3) Hard Coat for Molded Body The composition of the present invention can also be suitably used as a hard coat material for plastic molded bodies.
The composition of the present invention can be obtained by applying the composition of the present invention to the surface of a plastic molded body by, for example, spray coating or dip coating, and after drying, irradiating with active energy rays or heating to form a cured film.

Examples of the material of the plastic molded body include polyacrylic resins, polyphenylene oxide / polystyrene resins, polycarbonate resins, styrene copolymer resins, polystyrene resins, polyamide resins, and ABS resins.
These plastic moldings may be provided with a handle, a thin metal layer, or an easy adhesion layer. In addition, also when apply | coating the composition of this invention to the molded articles other than a plastic material, the application | coating method similar to a plastic molding can be used.

Further, as a method of protecting a plastic molded body with a cured film of the composition of the present invention, the film having the cured film formed thereon is placed on the plastic surface so that the cured film becomes the outermost surface before molding the plastic. There is also a method of pasting and then molding the plastic together with the film.
Examples of the method of attaching the film to the plastic surface include a method in which the film and the plastic are melt-bonded at a high temperature, and a method in which the film is bonded using an adhesive. Moreover, the method of sticking what formed the film which formed the hardened film on the molded object which shape | molded the plastic according to the external shape of this molded object is affixed.

When ultraviolet rays are used as a device for irradiating active energy rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, a short as a light generation source Examples thereof include an arc lamp, helium / cadmium laser, argon laser, sunlight, and LED.
In addition, when a cured film is formed by applying the composition of the present invention to a film substrate, it is preferable to use a flashing xenon-flash lamp because the influence of heat on the film substrate can be reduced. .

  On the other hand, when an electron beam is used, an electron beam accelerator having an acceleration voltage of 30 to 300 kV is preferable. When the article forming the protective layer is a film substrate such as a cellulose film, a polyester film, a polystyrene film, a polyamide film, or a polycarbonate film, yellowing or deterioration occurs due to electron beam irradiation. By setting it to -150 kV, yellowing and deterioration of a film base material can be prevented.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following, “part” means part by weight.

○ Production Example 1
In a reactor equipped with a stirrer and a thermometer, an acrylate mixture containing a tri isomer, a tetra isomer, and a compound M, and a mixture containing 77 wt% of the tri isomer and the tetra isomer (with an area ratio measured under the following conditions, 80 parts of toluene as a reaction solvent, 2.1 parts of methanesulfonic acid as an acid catalyst, and 2, as a polymerization inhibitor, 80 parts of a mixture containing tetramer: tetramer: compound M = 133.7: 100: 5.9) After charging 0.01 part of 6-di-tert-butyl-4-methylphenol hydroquinone monomethyl ether, the mixture was heated to 80 ° C. and reacted for 8 hours.
After completion of the reaction, 30 parts of water was added to the reaction solution, stirred at 20 ° C. and allowed to stand, and the lower layer (aqueous layer) was removed. The upper layer (organic layer) was stirred at 80 ° C. under reduced pressure of 1 to 400 mmHg for 4 hours, and toluene was distilled off to obtain 79 parts of a liquid acrylate mixture.

As a result of analyzing the obtained acrylate mixture by high performance liquid chromatography under the following conditions, the ratio of tri-isomer, tetra-isomer and compound M was as follows.
Compound M was separately analyzed by LC / MS [(UPLC) apparatus: Acquity UPLC system manufactured by Nippon Waters Co., Ltd., (MS) apparatus: Quattro premier API tandem quadrupole], and the above formula (1) In which R is a hydrogen atom.
○ Tri-body: Tetra-body: Compound M = 1.9: 100: 18.0
○ High-performance liquid chromatography measurement conditions:
High-performance liquid chromatograph: Acquity UPLC system manufactured by Japan Waters Co., Ltd. Column: Type: Silica gel modified with an alkyl group having 18 carbon atoms (Acquity BEH 1.7 μm C18) (Column: inner diameter: 2.1 mm × length) 150 mm), column temperature; 40 ° C.
Eluent: 0.03% by weight trifluoroacetic acid aqueous solution / acetonitrile = 60/40 (initial) → 50/50 (10 minutes) → 30/70 (15 minutes) → 0/100 (18-20 minutes), flow rate : 0.3 mL / min,
・ Detection wavelength of ultraviolet detector: 210 nm, sample concentration: 0.1 wt% acetonitrile solution, injection amount: 2 μL
-Tri-body peak retention time: 2.58 minutes, Tetra-body peak retention time: 6.17 minutes, Compound M peak retention time: 13.35 minutes * Tri-body peak area value as 100, The relative area value of the compound M peak was calculated.

Example 2
In a reactor equipped with a stirrer, a thermometer, and a water separator, 272 parts (2 mol) of pentaerythritol, 596 parts (8.27 mol) of acrylic acid, 460 parts of toluene as a reaction solvent, and paratoluenesulfonic acid (as an acid catalyst) In the following, 7 parts of PTS) and 1.4 parts of hydroquinone monomethyl ether (hereinafter referred to as MQ) were added as a polymerization inhibitor, and then heated to reflux at 80 kPa for 6 hours, and 115 parts (6.4 mol) of water was distilled off. I made it come out.
As a result of analyzing the reaction solution in the same manner as described above, the ratio of tri- and tetra-isomers was a mixture of 133.7: 100: 5.9 in area ratio.
To the reaction solution (1200 parts), 54 parts of PTS was added and stirred at 110 kPa at 80 kPa for 4 hours.
After completion of the reaction, 350 parts of toluene and 566 parts of a 10% aqueous sodium hydroxide solution were added to the reaction solution, stirred at 20 ° C. and allowed to stand, and the lower layer (aqueous layer) was separated to remove an excessive amount of acrylic acid. . Thereafter, 190 parts of water was added and stirred at 20 ° C., then allowed to stand, and the lower layer (aqueous layer) was removed. The upper layer (organic layer) was stirred at 80 ° C. under reduced pressure of 1 to 400 mmHg for 5 hours, and toluene was distilled off to obtain 650 parts of an acrylate mixture.
The obtained acrylate mixture was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 1.1: 100: 20.1

Example 3
In Example 2, the esterification reaction was carried out in the same manner as in Example 2 except that the amount of PTS was changed to 61 parts and the mixture was refluxed for 5 hours to distill 134 parts (7.4 mol) of water.
Further, heating was performed at 110 ° C. for 4 hours at 80 kPa, without adding an acid catalyst.
After completion of the reaction, the mixture was neutralized and washed with water in the same manner as in Example 2 to obtain 635 parts of an acrylate mixture.
The obtained acrylate mixture was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 1.0: 100: 21.4

◎ Comparative Example 1
In Example 2, the esterification reaction was carried out in the same manner as in Example 2 except that the amount of acrylic acid was changed to 760 parts (10.54 mol) and the amount of PTS was changed to 12 parts and refluxed for 6 hours. Part (7.4 mol) was distilled off.
Further, heating was performed at 110 ° C. for 4 hours at 80 kPa, without adding an acid catalyst.
After completion of the reaction, the mixture was neutralized and washed with water in the same manner as in Example 2 to obtain 640 parts of an acrylate mixture.
The obtained acrylate mixture was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 3.9: 100: 13.5

◎ Comparative Example 2
The mixture was refluxed for 6 hours under exactly the same conditions as in the esterification reaction of Example 2 to carry out the esterification reaction, and 115 parts (6.4 mol) of water was distilled off. In Comparative Example 2, only the esterification reaction was performed.
After completion of the reaction, the mixture was neutralized and washed with water in the same manner as in Example 2 to obtain 610 parts of an acrylate mixture.
The obtained acrylate mixture was analyzed by high performance liquid chromatography under the same conditions as described above. As a result, the proportions of tri-isomer, tetra-isomer and compound M were as follows.
Tri-form: Tetra-form: Compound M = 133.7: 100: 5.9

○ Evaluation The following evaluation was performed using the obtained acrylate mixture.

1) Curability 2 wt% photopolymerization initiator [1-hydroxycyclohexyl-phenyl ketone, trade name “Ilgar Cure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.] was added to and mixed with the acrylate mixture to prepare an ultraviolet curable composition. did.
The UV curable composition was applied to a bonderite steel plate to a thickness of 10 μm, and this was passed under a 80 W / cm condensing type high-pressure mercury lamp (focal length 30 cm) at a speed of 8 m / min using a conveyor, The curability was measured by evaluation with the number of passes required until the tack was eliminated.

2) Hardness A cured film that was completely cured in the curability test was used, and the pencil hardness was evaluated according to JIS K5600-5-4.

3) Volume shrinkage during curing (curing shrinkage)
In accordance with JISK0061-2001 (Method for measuring density and specific gravity of chemical products), the specific gravity at 25 ° C. of the composition was measured by a specific gravity bottle method.
The same UV curable composition as in the curing test was poured into a circular mold having a diameter of 4 cm and a depth of 1 mm, and irradiated with UV light for 150 seconds under a 60 W / cm parallel-light high-pressure mercury lamp (focal length 30 cm). It was. Then, the cured product was taken out from the mold, the front and back sides were reversed, and further UV irradiation was performed for 150 seconds under a 60 W / cm condensing high-pressure mercury lamp (focal length 30 cm). Curing in accordance with JISK6911-1995 The specific gravity of the object was measured.
From the specific gravity of the composition and the specific gravity of the cured product, the volume shrinkage ratio (curing shrinkage ratio) during curing was calculated according to the following formula.
Curing shrinkage (%) = (specific gravity of cured product−specific gravity of composition) / (specific gravity of cured product) × 100

4) Curling property 100 parts of acrylate mixture, 5 parts of photopolymerization initiator 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [Ciba Specialty Chemicals Co., Ltd. Product name “Ilgar Cure 907” and 50 parts of toluene were added and mixed to prepare an ultraviolet curable composition.
The ultraviolet curable composition was applied to a thickness of 4 μm on a triacetyl cellulose film having a thickness of 100 μm, and left in an oven at 80 ° C. for 2 minutes to evaporate toluene. Thereafter, UV irradiation was performed under an 80 W / cm parallel light type high-pressure mercury lamp (focal length: 30 cm) to perform a curing treatment (irradiation intensity: 1000 mJ / cm ² ).
The cured film was cut into 10 cm × 10 cm and left in a room at a temperature of 23 ° C. and a humidity of 50% for 1 hour. Thereafter, the film was placed on a horizontal glass plate, the height of each of the four sides that floated was measured, and the total of the measured values (unit: mm) of the four sides was listed in Table 2 as curl properties.

5) Flexibility Flexibility was evaluated according to JISK5400-1990. However, the test plate was obtained by cutting the film after evaluating the curling property into 5 cm × 10 cm. The minimum diameter of the mandrel that withstood the bending is listed in Table 2.

Curable hard coat agent composition of the present invention, by irradiation of an active energy ray, or curable by heating are those useful for the hard coat application is a coating of plus chip click, various industries that use them It can be usefully used in the field.

Claims (2)

A curable hard coat agent composition comprising the following (meth) acrylate mixture.
(Meth) acrylate mixture: pentaerythritol tri (meth) acrylate (hereinafter referred to as “tri-form”), pentaerythritol tetra (meth) acrylate (hereinafter referred to as “tetra-form”) and An area ratio of a compound (hereinafter referred to as “compound M”) obtained by Michael addition to a (meth) acryloyl group was measured by liquid chromatography under the following conditions. Containing mixture.
Tri-form: Tetra-form: Compound M = 0.1-2.0: 100: 15.0-50.0
Liquid chromatography measurement condition equipment: high-performance liquid chromatograph (HPLC), detector: ultraviolet detector, column type: column consisting of silica gel (particle diameter: 1.7 μm) modified with an alkyl group having 18 carbon atoms (particle diameter: 1.7 μm) ID: 2.1 mm × length: 150 mm), column temperature: 40 ° C., eluent: 0.03% by weight trifluoroacetic acid aqueous solution / acetonitrile = 60/40 (initial) → 50/50 (10 minutes) → 30 / 70 (15 minutes) → 0/100 (18-20 minutes) The curable hard coat agent composition according to claim 1, wherein the (meth) acrylate mixture is obtained by heating and stirring a tri-form and a tetra-form in the presence of an acid catalyst.