JP2014084360A - Active energy ray-curable undercoat composition, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable undercoat composition which exhibits excellent coating suitability to a plastic base material and whose cured film obtained exhibits excellent adhesiveness, become easily wetted by various coating liquids, has excellent adhesiveness with an organic or inorganic layer to be formed thereon, and does not deteriorate hardness or scratch resistance of the organic or inorganic layer to be formed thereon.SOLUTION: The active energy ray-curable undercoat composition contains a reaction product (A) obtained by reacting an alkoxysilane compound (a1) represented by the general formula (1) with fine particles of an inorganic oxide (A2) in the presence of water and an organic solvent: (P-SiO)(P-Si(R)O)(OR)(1); in the general formula (1), P is a maleimide group represented by a specific general formula; Ris a hydrogen atom or a monovalent organic group; Ris a monovalent organic group; a is 0 or a positive number (0≤a<1); and z is a positive number (0.1≤z≤2).

Description

  The present invention relates to an active energy ray-curable undercoat composition containing inorganic oxide fine particles whose surface is modified with a maleimide group, and a laminate having the cured layer.

Plastic materials are widely used in various fields such as home appliances, automobile materials, and building materials because they are inexpensive, lightweight, and have excellent processability. In addition, plastic materials having excellent transparency are used as optical materials in liquid crystal displays, touch panels, building materials, and the like.
When plastic is used as an optical material, an optical function is often added on a plastic substrate or a hard coat treatment is performed for the purpose of surface protection or the like. Specifically, a lens sheet, an antiglare sheet, and the like are manufactured by a manufacturing method in which a mold shape is transferred onto a plastic substrate using an active energy ray-curable composition. In addition, a method of applying and curing an active energy ray-curable composition and providing a hard coat layer is widely practiced. In many cases, functions such as antifouling property and antistatic property are added to the hard coat layer.
The hard coat layer can be formed not only by applying a liquid curable resin and curing it, but also by pre-making a hard coat film inside the mold during plastic molding and integrating it with the product surface. In recent years, this method has been implemented.
The optical layer formed on the plastic substrate is not only an organic layer formed from an organic material such as a curable resin, but also an inorganic formed from a metal or metal oxide formed by vapor deposition or sputtering. Can be a layer.
As described above, there are various optical materials for forming various layers using a plastic material as a base material. In any case, the adhesion between the plastic base material and the other layer is important.
In order to increase the adhesion between the plastic substrate and the functional layer such as the hard coat or optical layer, or to provide another function such as weather resistance, an underlayer is provided between the functional layer and the plastic substrate. A coat layer (primer layer) may be provided. Here, as the undercoat layer, an active energy ray-curable composition having excellent productivity may be used (Patent Document 1).
However, when the plastic substrate is a hardly adhesive material such as a cycloolefin polymer, the adhesion between the substrate and the undercoat layer was insufficient. In addition, when a leveling agent was used to obtain the smoothness of the undercoat layer, the coatability of the upper layer became poor, and the adhesion with the upper layer became poor. Further, when the hardness of the undercoat layer is low, problems such as poor hard coat performance occur when the upper layer is a hard coat.

JP 2004-82743 A

  The present invention is excellent in coating property to a plastic substrate, the obtained cured product is excellent in adhesion, easily wetted with various coating solutions, and adherence to an organic layer or an inorganic layer formed on the cured product. It is an object of the present invention to provide an active energy ray-curable undercoat composition that is excellent in resistance and does not deteriorate the hardness and scratch resistance of an organic layer or inorganic layer formed on a cured product.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a reaction product obtained by reacting an alkoxysilane compound having a specific structure having a maleimide group and inorganic oxide fine particles in the presence of water and an organic solvent. It has been found that a composition containing the composition can solve the above problems.

  According to the composition of the present invention, it is excellent in coating property and adhesion to a plastic substrate, easily wetted with various coating liquids, and excellent in adhesion with an organic layer or an inorganic layer formed on a cured product. Even if the layer formed on the cured product is a hard coat layer, the scratch resistance is not lowered.

The present invention relates to an alkoxysilane compound (a1) represented by the following general formula (1) (hereinafter simply referred to as “(a1)”) and inorganic oxide fine particles (a2) (hereinafter simply referred to as “(a2)”). Is a reaction product (A) obtained by reacting in the presence of water and an organic solvent (hereinafter, simply referred to as “component (A)”).

(P-SiO _3/2 ) _1-a (P-Si (R ⁰ ) O _2/2 ) _a (O _1/2 R ³ ) _z (1)

However, in the general formula (1), P represents a group represented by the following general formula (2), R ³ represents a hydrogen atom or a monovalent organic group, R ⁰ represents a monovalent organic group, a is 0 or a positive number and 0 ≦ a <1 is satisfied, z is a positive number and 0.1 ≦ z ≦ 2 is satisfied, and P, R ⁰ and R ^{3 in} one molecule are each two types The above different groups may be included, and R ⁰ and R ³ in one molecule may be the same group or different groups.

Hereinafter, the components (a1), (a2) and (A) will be described in detail. Then, other components, an undercoat formation method, a laminated body, and a use are demonstrated.
In the present specification, an acryloyl group or a methacryloyl group is represented as a (meth) acryloyl group, and an acrylate or methacrylate is represented as a (meth) acrylate.

1. (A1)
1-1. Definition of (a1) (a1) which is a raw material of the component (A) of the present invention is a compound represented by the following general formula (1).
(A1) means either a condensate of alkoxysilane obtained by partially hydrolyzing and condensing alkoxysilane, or a mixture of this condensate and alkoxysilane monomer, as will be described in detail later.

(P-SiO _3/2 ) _1-a (P-Si (R ⁰ ) O _2/2 ) _a (O _1/2 R ³ ) _z (1)

However, in the general formula (1), P represents a group represented by the following general formula (2), R ³ represents a hydrogen atom or a monovalent organic group, R ⁰ represents a monovalent organic group, a is 0 or a positive number and 0 ≦ a <1 is satisfied, z is a positive number and 0.1 ≦ z ≦ 2 is satisfied, and P, R ⁰ and R ^{3 in} one molecule are each two types The above different groups may be included, and R ⁰ and R ³ in one molecule may be the same group or different groups.

In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R ¹ and R ² are combined to form a 5-membered member. The hydrocarbon group which forms a ring or a 6-membered ring is represented.
As an alkyl group, a C1-C4 alkyl group is preferable.
As the alkenyl group, an alkenyl group having 2 to 4 carbon atoms is preferable.
A phenyl group etc. can be mentioned as an aryl group.
The hydrocarbon group is one to form a 5- or 6-membered _{ring, -CH 2 CH 2 CH 2 -} , - CH 2 CH 2 CH 2 CH 2 -, - CH = CH-CH 2 CH 2 - Etc.

  Preferred specific examples of the maleimide group in the general formula (2) are shown in the following formulas (5) to (10). In the formula (9), X represents a chlorine atom or a bromine atom. Moreover, Ph in Formula (10) represents a phenyl group.

Among these, as R ¹ and R ² , both are hydrogen atoms, one is a hydrogen atom and the other is an alkyl group, both are alkyl groups, or a saturated hydrocarbon group in which each forms a carbocycle. It is preferable because it is excellent in curability by irradiation with active energy rays.
Further, as R ¹ and R ² , one is a hydrogen atom and the other is an alkyl group, or a saturated hydrocarbon group that forms a carbocyclic ring by combining each of them is excellent in the curability of the composition and is cured. The hard coat layer when the hard coat layer is formed on the product is more preferable in that it has excellent scratch resistance.
As R ¹ and R ² , it is particularly preferable that one is a hydrogen atom and the other is an alkyl group.
Moreover, it is preferable that the alkyl group in R < ¹ > and R < ² > is a C1-C4 alkyl group.

In the general formula (2), the divalent organic group represented by R is arbitrary as long as it is a divalent organic group. Preferred are divalent saturated hydrocarbon ^{group, -A 1 -OCONH-A 2 -} , - A 3 -S-A 2 -, - A 3 -NH-A 2 - and the like. Here, A ¹ and A ² represents a divalent saturated hydrocarbon group having 1 to 6 carbon atoms. The divalent saturated hydrocarbon group may be linear or branched. A ³ represents a structure after addition of a thiol or an amine to a divalent organic group having an ethylenically unsaturated group at the terminal, specifically, a divalent saturated hydrocarbon group and —A ⁵ OCOCH (A ⁶ ) CH ₂ — can be mentioned. A ⁵ means a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and A ⁶ means a hydrogen atom or a methyl group.

  As R, the cured product of the composition is excellent in scratch resistance and ultraviolet (UV) resistance, and among these, a divalent saturated hydrocarbon group is preferable, and a divalent having 1 to 6 carbon atoms. A saturated hydrocarbon group is more preferable, and a linear divalent saturated hydrocarbon group having 3 to 6 carbon atoms is particularly preferable.

In the general formula (1), R ³ represents a hydrogen atom or a monovalent organic group.
The monovalent organic group for R ³ is preferably a monovalent organic group having 1 to 8 carbon atoms. Specific examples include an alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 1 to 8 carbon atoms, and other organic groups having 1 to 8 carbon atoms composed of C, H, and O atoms.
Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the alkoxyalkyl group having 1 to 8 carbon atoms include a 1-methoxy-2-propyl group and a 2-methoxyethyl group. Other examples of the organic group having 1 to 8 carbon atoms composed of C, H, and O atoms include groups having a structure in which a hydroxyl group is removed from diacetone alcohol.
The monovalent organic group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group in that the cured product of the composition has excellent scratch resistance and UV resistance. An alkyl group having 1 to 3 carbon atoms is more preferable.

In the general formula (1), examples of the monovalent organic group of R ⁰ include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group, and an aromatic group such as a phenyl group.
Furthermore, as R ⁰ , an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable and particularly preferable in that the cured product of the composition has excellent scratch resistance. Is a methyl group or an ethyl group.

In the general formula (1), a is 0 or a positive number and satisfies the condition of 0 ≦ a <1, and z is a positive number and satisfies 0.1 ≦ z ≦ 2.
a is the average ratio of (P—Si (R ⁰ ) O _2/2 ) units in [(P—SiO _3/2 ) _1-a (P—Si (R ⁰ ) O _2/2 ) _a ] units. Z means the average value of (O _1/2 R ³ ) units in the entire (a1).
The range of a is 0 ≦ a <1, and preferably 0 ≦ a ≦ 0.5. It is preferable for a to be 0.5 or less because the cured product of the composition has excellent scratch resistance.
In the present invention, as (a1), a compound of a = 0 is preferable because of excellent scratch resistance.
The range of z is 0.1 ≦ z ≦ 2, preferably 0.6 ≦ z ≦ 2, and more preferably 0.6 ≦ z ≦ 1.5. When z is 0.1 or more, the surface modification of colloidal silica is made sufficient, and the cured product has excellent scratch resistance.
The values of a and z can be obtained from the integration ratio of hydrogen atoms by measuring the ¹ H-NMR spectrum of (a1).

Further, P, R ⁰ and R ³ in one molecule may contain two or more different groups. That is, each unit of (P—SiO _3/2 ) _1-a unit, (P—Si (R ⁰ ) O _2/2 ) _a unit, and (O _1/2 R ³ ) unit in formula (1) is Each of them may have two or more different units in one molecule. In addition, P of (P—SiO _3/2 ) _1-a unit and P of (P—Si (R ⁰ ) O _2/2 ) _a unit in one molecule are the same or different. May be.
Further, R ⁰ and R ³ in one molecule may be the same group or different groups.

As a weight average molecular weight of (a1), 400-10,000 are preferable, More preferably, it is 500-5,000.
In the present invention, the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene.

(A1) is preferably a compound represented by the following general formula (3).

(P′—SiO _3/2 ) (O _1/2 R ³ ′) _z (3)

However, in the general formula (3), P 'represents a group represented by the following general formula (4), R ^3' represents an organic group or a hydrogen atom monovalent C1-8, z is positive And 0.1 ≦ z ≦ 2.
As what contains the structural unit represented by the said General formula (3), what is a weight average molecular weight 500-5,000 is the most preferable.

In the general formula (4), one of R ⁴ and R ⁵ is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms, or both are alkyl groups having 1 to 6 carbon atoms, or It represents that it is a saturated hydrocarbon group that forms a 6-membered ring, and R ⁶ represents a divalent saturated hydrocarbon group having 2 to ⁶ carbon atoms.

As R ⁴ and R ⁵ , one is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms, or a saturated hydrocarbon group that forms a 6-membered ring together to improve curability of the composition. It is more preferable because it is excellent and the cured product has excellent scratch resistance.
As R ⁴ and R ⁵ , it is particularly preferable that one is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms.
In R < ⁴ > and R < ⁵ >, as a C1-C6 alkyl group, a C1-C4 alkyl group is more preferable at the point which is excellent in the sclerosis | hardenability of a composition.
R ⁶ represents a divalent saturated hydrocarbon group having 2 to ⁶ carbon atoms, and may be linear or branched. Examples of the linear saturated hydrocarbon group having 2 to 6 carbon atoms include ethylene group, 1,3-propylene group, 1,4-butylene group, 1,5-pentanediyl group, 1,6-hexanediyl group and the like. it can. Examples of the branched alkylene group having 2 to 6 carbon atoms include 1,2-propylene group, 1,2-butylene group, 1,3-butylene group, 2,3-butylene group, 1,3-pentanediyl group, 2, Examples include 4-pentanediyl group, 2,5-hexanediyl group, 2-methyl-1,3-propylene group, 2-ethyl-1,3-propylene group, 3-methyl-1,5-pentanediyl group and the like.
R ⁶ is particularly preferably a linear divalent saturated hydrocarbon group having 3 to 6 carbon atoms.

In the general formula (3), z represents 0.1 ≦ z ≦ 2.
The range of z is 0.1 ≦ z ≦ 2, preferably 0.6 ≦ z ≦ 2, and more preferably 0.6 ≦ z ≦ 1.5. When z is 0.1 or more, the surface modification of colloidal silica is made sufficient, and the cured product has excellent scratch resistance.
As described above, the value of z can be obtained from the integration ratio of hydrogen atoms by measuring the ¹ H-NMR spectrum of (a1).
Incidentally, P and R ³ in one molecule may contain two or more different groups.

1-2. Various methods can be adopted as the production method (a1) of (a1).
In the following, first, a preferable manufacturing method will be described for the case of a = 0 in the general formula (1), and then the case of a ≠ 0 will be described.

1-2-1. In the case of a = 0, a preferable production method of the compound in which a = 0 in the formula (1), that is, the compound of the following general formula (1) ′ will be described.

(P-SiO _3/2 ) (O _1/2 R ³ ) _z (1) ′

As a preferable production method in this case, an aminoalkyltriglyceride represented by the following general formula (12) is added to a carboxylic acid anhydride having a double bond represented by the following general formula (11) in the presence of an organic solvent. An example is a method in which an alkoxysilane is added to form an amic acid, which is then ring-closed by heating to form a maleimide group, and water generated by the ring-closing reaction is consumed in the hydrolysis reaction of the alkoxy group.
This method is particularly preferable in that (a1) can be easily produced using readily available raw materials.

In the formula (11), R ¹ and R ² are as defined above.

In the formula (12), R and R ³ are as defined above.
Preferable examples of R and R ³ are the same as those described above. In particular, R is preferably R ⁶ (a divalent saturated hydrocarbon group having 2 to ⁶ carbon atoms).

Hereinafter, this reaction will be described in more detail.
First, an amino group of an aminoalkyltrialkoxysilane is added to a carboxylic acid anhydride having a double bond to produce an amic acid (hereinafter referred to as AMA) [Reaction Formula (1)].

  Next, when the solution containing AMA is heated, the ring closure reaction proceeds and a maleimide group is generated. At this time, since water is simultaneously generated, the alkoxy group is hydrolyzed, and then the condensation reaction proceeds [Reaction Formula (2)].

  Here, the value of z is 1 when the ring-closing reaction is complete and all the generated water is consumed in the hydrolysis and condensation reaction of alkoxysilane.

In the said manufacturing method, as an organic solvent, what melt | dissolves AMA and does not react with a raw material is preferable. Specifically, aromatic compounds such as toluene and xylene are preferable. However, since the reaction between the acid anhydride and the amino group is very fast, polar solvents such as alcohols and esters can also be used.
The temperature for the ring closure reaction is preferably in the range of 70 to 150 ° C.
When a compound that hardly dissolves water, for example, an aromatic compound, is used as the organic solvent, it is preferable to remove the solvent after completion of the reaction. The proportion of the carboxylic acid anhydride having a double bond and the aminoalkyltrialkoxysilane is preferably equimolar. As the carboxylic acid anhydride and aminoalkyltrialkoxysilane having a double bond, a plurality of types can be used in combination.

During the reaction, a polymerization inhibitor is preferably used for the purpose of preventing polymerization of the maleimide group of the raw material or product, and oxygen-containing gas such as air is preferably introduced into the reaction solution.
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, Examples thereof include N-nitrosophenylhydroxylamine, ammonium salt of N-nitrosophenylhydroxylamine, aluminum salt of N-nitrosophenylhydroxylamine, copper dibutyldithiocarbamate, copper chloride, copper sulfate and the like.

1-2-2. When a ≠ 0 Next, a preferred method for producing a compound in which a ≠ 1 in the formula (1) will be described.
Also in this case, the same production method as described above is preferable, and the carboxylic acid anhydride having a double bond represented by the general formula (11) is represented by the general formula (12) in the presence of an organic solvent. An aminoalkyltrialkoxysilane and an aminoalkyldialkoxysilane represented by the following general formula (13) are added to form an amic acid, which is then ring-closed by heating to form a maleimide group. The method of making it consume by hydrolysis reaction of this is mentioned.

In the formula (13), R, R ⁰ and R ³ are as defined above.
Preferable examples of R, R ⁰ and R ³ are the same as those described above. In particular, R is preferably R ⁶ (a divalent saturated hydrocarbon group having 2 to ⁶ carbon atoms).

  The reaction method and reaction conditions are as described in 1-2-1. Same as above.

2. (A2)
In (a2) (inorganic oxide fine particles), as the types of inorganic oxides, oxides of various inorganic compounds and metal oxides can be used. Specifically, silica, alumina, titanium oxide, zinc oxide, Examples thereof include tin oxide, indium oxide, zirconium oxide, iron oxide, vanadium oxide, cerium oxide, antimony oxide, and indium-doped tin oxide. Among these, silica, alumina, titanium oxide, zinc oxide, and tin oxide are preferable, and silica is more preferable because it is excellent in colorless transparency, scratch resistance, price, and the like.
These particles can be used alone or in combination of two or more.

  As described above, silica is more preferable as (a2), and the silica may be particles having silica as a main component, and may contain other components than silica. Components other than silica include inorganic oxides such as alkali metal oxides, alkaline earth metal oxides, aluminum oxide, titanium oxide, iron oxide, zirconium oxide, zinc oxide, cerium oxide, boron oxide, tin oxide and phosphorus oxide. Can mention

The average particle size of (a2) is preferably in the range of 1 to 200 nm, more preferably 1 to 100 nm, and particularly preferably 5 to 50 nm from the viewpoint of excellent transparency and scratch resistance. When the average particle size is 1 nm or more, handling and mixing / dispersion are facilitated. On the other hand, when the average particle size is 200 nm or less, even when mixed and dispersed in the composition, it does not settle, and the composition and its cured product are transparent. Will not drop.
In addition, in this invention, an average particle diameter means the value based on the specific surface area measured by BET method.

The specific surface area of (a2) is preferably set to a value within the range of 15 to 3000 m ² / g, more preferably 30 to 3000 m ² / g. By setting the specific surface area of the particles to 15 m ² / g or more, when mixed and dispersed in the composition, the particles do not settle, and the transparency of the composition and its cured product does not decrease. By setting the value to 3000 m ² / g or less, handling and mixing / dispersing are facilitated.

  The shape of the particles (a2) is not particularly limited, but is preferably at least one shape selected from the group consisting of spherical, hollow, porous, rod-like, plate-like, fibrous, and indefinite shape. . However, it is more preferable to use spherical particles from the viewpoint of better dispersibility.

The state of use of the particles (a2) is not particularly limited. For example, the particles can be used in a dry state, or can be used in a state dispersed in water or an organic solvent.
In the present invention, a liquid in which fine silica particles are dispersed using a dispersion solvent, that is, colloidal silica is particularly preferable for the purpose of pursuing transparency.

  Here, when the dispersion solvent is an organic solvent, methanol, ethanol, isopropyl alcohol, ethylene glycol, butanol, propylene glycol monomethyl ether, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and dimethylformamide are used. be able to. Among these, alcohols such as methanol and isopropyl alcohol, and ketones such as methyl ethyl ketone are preferable. Moreover, you may use as an organic solvent other than these which is compatible with these organic solvents, or a mixture with water.

3. Component (A) The component (A) in the present invention is a product obtained by reacting the above (a1) and (a2) in the presence of water and an organic solvent. In the present invention, the component (A) means the product itself excluding water and organic solvent used in the reaction.
As (a1) and (a2), a plurality of types of compounds, condensates, and fine particles may be contained. In addition, the component (A) includes not only inorganic oxide fine particles surface-modified with maleimide groups represented by the general formula (2), but also hydrolyzed maleimide alkoxysilane (a1) containing no inorganic oxide fine particles. A decomposition condensate may be contained, and these are defined as the component (A).

The amount ratio of (a1) and (a2) for obtaining the component (A) is not particularly limited, but (a2) is 1-1000 parts by weight with respect to 100 parts by weight of (a1). More preferably, it is 5-500 weight part, More preferably, it is 10-200 weight part.
(A1) By setting the number of charged parts of (a2) to 1 to 1000 parts by weight with respect to 100 parts by weight, the scratch resistance can be improved.

  The amount of water charged into the reaction system is preferably 1 to 30 mol, more preferably 1 to 15 mol, and even more preferably 2 to 10 mol with respect to 1 mol of the alkoxy group. The surface of the inorganic oxide fine particles can be effectively modified by adjusting the amount of water charged to 1 to 30 mol with respect to 1 mol of the alkoxy group.

  As the organic solvent, those capable of dissolving (a1) are preferable. In addition, it is also preferable to mix and dissolve two or more types of solvents that cannot dissolve (a1) with one type. Further, it is preferable to dissolve water in the reaction system. Furthermore, when (a2) is a uniformly transparent colloid solution, it is preferable to select a solvent in which the inorganic oxide fine particles do not aggregate.

  Specific examples of preferable organic solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Examples include ethyl ether, diacetone alcohol, propylene glycol monoacetate, ethylene glycol monoacetate, diethylene glycol monoethyl ether acetate, and N-methylpyrrolidone.

  Although the reaction temperature for obtaining (A) component changes with the presence or absence of a catalyst or the presence or absence of pressurization, the range of 0-200 degreeC is preferable, More preferably, it is 20-180 degreeC, More preferably, it is 40-160 degreeC, Especially Preferably it is 60-140 degreeC.

  After completion of the reaction, the water contained in the reaction system is preferably distilled off by heating, reduced pressure or the like. At this time, it is preferable to add an organic solvent having a boiling point higher than that of water.

The component (A) can be produced without a catalyst, but an acid catalyst or an alkali catalyst may be added.
Specific examples of the acid catalyst include acetic acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid.
Specific examples of the alkali catalyst include potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide. However, the component (A) obtained without a catalyst is preferable because there is no problem of a decrease in physical properties of the cured product due to the catalyst.
In the reaction, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization of the maleimide group of the raw material or product, and oxygen-containing gas such as air may be introduced into the reaction solution.

  Specific examples of the polymerization inhibitor include the above 1-2. Examples thereof include the same compounds as mentioned above.

  Component (A) may contain a condensate obtained by cocondensation of a hydrolyzable silane compound different from maleimide alkoxysilane (a1). Further, not only maleimide alkoxysilane (a1) but also a hydrolyzable silane compound different from this may contain surface-modified inorganic oxide fine particles.

Specific examples of the hydrolyzable silane compound different from (a1) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3 -(Meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3 -Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-isocyanatopropyl Limethoxysilane, 3-isocyanatopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, p-styryl Trimethoxysilane, p-styryltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, 3-[(3-ethyloxetane-3-yl) methoxy] propyltrimethoxysilane, 3-[(3-ethyloxetane-3-yl) methoxy] propyltriethoxysilane , 3-triethoxysilyl-N- (1, -Dimethyl-butylidene) propylamine, dimethyldimethoxysilane, dimethyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxy Examples include silane, tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, trimethoxysilane, and triethoxysilane.
Among these, the silane compound which does not have an aromatic group is preferable at the point which the hardened | cured material obtained is excellent in a weather resistance. Furthermore, preferred compounds are alkyltrialkoxysilanes, silane compounds having a (meth) acryloyloxy group having a reactive group, silane compounds having an epoxy group, and silane compounds having an oxetanyl group.

4). TECHNICAL FIELD The present invention relates to an active energy ray-curable undercoat composition containing the aforementioned component (A).
Since the component (A) has a maleimide group, it does not contain a photopolymerization initiator by irradiation with active energy rays, or has excellent curability with a small amount.
In addition to the essential component (A), various components (hereinafter referred to as “other components”) can be blended in the composition of the present invention.
Preferred examples of other components include compounds other than the component (A) having two or more ethylenically unsaturated groups [hereinafter referred to as “component (B)”], photopolymerization initiators [hereinafter referred to as “(C)”. Component ”and an organic solvent (D).
Hereinafter, the components (B) to (D) and other components other than these will be described.

4-1. Component (B) The component (B) is a compound other than the component (A) having two or more ethylenically unsaturated groups.
Examples of the ethylenically unsaturated group in component (B) include a (meth) acryloyl group, a maleimide group, an amide group, and a vinyl group, with a (meth) acryloyl group being preferred.
Examples of the component (B) include a compound having two or more (meth) acryloyl groups [hereinafter referred to as “polyfunctional (meth) acrylate”], a compound having two or more maleimide groups (hereinafter referred to as “polyfunctional”). And a compound having at least one (meth) acryloyl group and at least one maleimide group (hereinafter referred to as “maleimide (meth) acrylate”).
The total number of ethylenically unsaturated groups in component (B) is preferably 2 to 10, more preferably 3 to 10, and further preferably 3 to 6.

Examples of the polyfunctional (meth) acrylate include the following compounds.
Di (meth) acrylate of bisphenol A alkylene oxide adduct, di (meth) acrylate of alkylene oxide adduct of bisphenol F, di (meth) acrylate of alkylene oxide adduct of bisphenol Z, alkylene oxide adduct of bisphenol S Di (meth) acrylate, di (meth) acrylate of alkylene oxide adduct of thiobisphenol, di (meth) acrylate of bisphenol A, di (meth) acrylate of bisphenol F, di (meth) acrylate of bisphenol Z, bisphenol S Di (meth) acrylate, di (meth) acrylate of thiobisphenol, tricyclodecane dimethylol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonane Di (meth) acrylate, glycerin di (meth) acrylate, di (meth) acrylate of glycerin alkylene oxide adduct, dimer acid diol di (meth) acrylate, cyclohexane dimethylol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, trimethylolpropane alkylene oxide adduct tri (meth) acrylate, pentaerythritol tri- and tetraacrylate, pentaerythritol alkyle Trioxides and tetraacrylates of oxide adducts, triacrylates of alkylene oxide adducts of isocyanuric acid, ε-caprolactone modified tris ((meth) acryloxyethyl) isocyanurate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa and Examples thereof include pentaacrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and a silicone resin having a (meth) acryloyl group at the terminal.

  As a polyester (meth) acrylate, the dehydration condensate of a polyester polyol and (meth) acrylic acid is mentioned. Polyester polyols include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, and trimethylolpropane, and Examples include reactants from polyols such as these alkylene oxide adducts and acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or anhydrides thereof.

  As epoxy (meth) acrylate, (meth) acrylic acid adduct of bisphenol A type epoxy resin, (meth) acrylic acid adduct of hydrogenated bisphenol A type epoxy resin, (meth) acrylic of phenol or cresol novolac type epoxy resin Acid addition products, (meth) acrylic acid addition products of biphenyl type epoxy resins, (meth) acrylic acid addition products of diglycidyl ether of polyethers such as polytetramethylene glycol, (meth) acrylic acid addition of diglycidyl ether of polybutadiene Products, (meth) acrylic acid adducts of polybutadiene internal epoxidized products, (meth) acrylic acid adducts of silicone resins having epoxy groups, (meth) acrylic acid adducts of limonene dioxide, 3,4-epoxycyclohexylmethyl- 3,4-epoxy Cyclohexanecarboxylate (meth) acrylic acid adduct and the like.

Examples of urethane (meth) acrylate include compounds obtained by addition reaction of organic polyisocyanate compound and hydroxyl group-containing (meth) acrylate, and compounds obtained by addition reaction of organic polyisocyanate compound, polyol and hydroxyl group-containing (meth) acrylate. It is done.
Here, examples of the polyol include a low molecular weight polyol, a polyether polyol, a polyester polyol, and a polycarbonate polyol.
Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, and glycerin.
Examples of the polyether polyol include polypropylene glycol and polytetramethylene glycol.
As the polyester polyol, a reaction product of these low molecular weight polyols and / or polyether polyols and an acid component such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or a dibasic acid or its anhydride. Is mentioned.
Examples of the organic polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
Examples of the hydroxysil group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxyalkyl (meta) such as modified caprolactone thereof. ) Acrylate, pentaerythritol tri (meth) acrylate, diisocyanate 3-mole adduct of isocyanuric acid di (meth) acrylate, hydroxyl group-containing polyfunctional (meth) acrylate such as dipentaerythritol penta (meth) acrylate, etc. It is done.

As the polyfunctional maleimide compound, various compounds can be used as long as they are compounds having a maleimide group and compounds other than the component (A). In this case, the maleimide group is preferably the same group as the maleimide group in the formula (2).
As the polyfunctional maleimide compound, for example, a urethane compound obtained by adding N- (2-hydroxyethyl) citraconimide to hexamethylene diisocyanate, a urethane compound obtained by adding N- (2-hydroxyethyl) citraconimide to isophorone diisocyanate, Urethane compound obtained by addition reaction of N- (2-hydroxyethyl) citraconimide and diol such as polyester diol and isophorone diisocyanate, MIA-200 manufactured by Dainippon Ink Co., Ltd., which is a compound having two maleimide groups Is mentioned.

  Specific examples of maleimide (meth) acrylate include N- (2- (meth) acryloxyethyl) tetrahydrophthalimide.

As the component (B) of the present invention, a compound having 3 or more (meth) acryloyl groups is preferable.
Examples of the compound include dipentaerythritol hexa and pentaacrylate, triacrylate of ethylene oxide 3 mol adduct of isocyanuric acid, pentaerythritol tri and tetraacrylate.
Furthermore, as the compound having 3 or more (meth) acryloyl groups, urethane (meth) acrylate having 3 or more (meth) acryloyl groups [hereinafter referred to as component (B2)] is preferable.
As a suitable example of the component (B2), a urethane obtained by adding a diisocyanate compound (b-1) and a compound (b-2) having one hydroxyl group and two or more (meth) acryloyl groups ( (Meth) acrylate; urethane obtained by adding a compound (b-3) having three or more isocyanate groups and a compound (b-4) having one hydroxyl group and one (meth) acryloyl group (meta) ) Acrylate; urethane (meth) acrylate obtained by adding (b-3) and (b-2); and urethane (meth) acrylate obtained by adding a diol or a polyol compound when these are synthesized And the like.
Specific examples of (b-1) include hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, norbornane diisocyanate methyl, diphenylmethane diisocyanate (MDI), hydrogenated MDI and the like.
Specific examples of (b-2) include di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meta) of adducts of isocyanuric acid with 3 moles of ethylene oxide. ) Acrylate and the like.
Specific examples of (b-3) include hexamethylene diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, norbornane diisocyanate methyl, diphenylmethane diisocyanate (MDI), and hydrogenated MDI. Examples include a monomer and a biuret type trimer. Moreover, the polyisocyanate compound etc. which added diisocyanate compounds, such as hexamethylene diisocyanate, to polyols, such as a trimethylol propane, are mentioned.
Specific examples of (b-4) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone-modified products thereof.

  When the undercoat layer of the present invention is formed under the hard coat layer, preferred examples of the component (B2) include hexamethylene diisocyanate and / or isophorone diisocyanate, pentaerythritol tri (meth) acrylate and / or isocyanuric acid. And urethane (meth) acrylate obtained by addition reaction of di (meth) acrylate of 3 moles of ethylene oxide adduct. Another preferred example is urethane (meth) acrylate obtained by addition reaction of hexamethylene diisocyanate nurate-type trimer and hydroxyethyl (meth) acrylate and / or hydroxybutyl (meth) acrylate. These compounds are particularly preferred because of their adhesion to the plastic substrate, the scratch resistance of the hard coat layer formed thereon, and the difficulty of cracking when bent.

As the component (B), two or more compounds can be used in combination.
(B) As a compounding ratio of a component, it is 0-95 parts with respect to 100 weight part of total solids in a composition, More preferably, it is 10-90 weight part, More preferably, it is 20-85 weight part. .
By blending the component (B), it is possible to improve crack resistance and scratch resistance when bent. Moreover, the adhesiveness and coating property to a plastic base material can be made favorable by setting it as 95 weight part or less.

4-2. Component (C) As described above, the composition of the present invention can be cured without adding a photopolymerization initiator. For the purpose of increasing the curing rate, the component (C) (photopolymerization initiator) ) Can also be added.
Specific examples of the component (C) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl Acetophenone photopolymerization initiators such as phenyl} -2-methyl-propan-1-one; such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4′-methyl-diphenylsulfide Benzophenone photopolymerization initiator; thioxanthone photopolymerization initiator such as 2,4-diethylthioxanthone and isopropylthioxanthone, methylbenzoylformate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid, and Α-ketoester photopolymerization initiators such as 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) pheny Phosphine oxide photopolymerization initiators such as phosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and Benzoin photopolymerization initiators such as benzoin isobutyl ether; titanocene photopolymerization initiators; 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfinyl) propane-1 An acetophenone / benzophenone hybrid photopolymerization initiator such as -one; an oxime ester photopolymerization initiator such as 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1,2-octanedione; and Camphorki Non etc. are mentioned.

As the component (C), among the above-described photopolymerization initiators, a thioxanthone photopolymerization initiator or a benzophenone photopolymerization initiator can exhibit excellent adhesion to difficult-to-adhere materials even with a small amount of active energy ray irradiation. This is preferable.
Specific examples include 2,4-diethylthioxanthone, isopropylthioxanthone, benzophenone, 4-methylbenzophenone, methyl-2-benzoylbenzoate, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-. And methyl-diphenyl sulfide.

As the component (C), two or more kinds of compounds can be used in combination.
The blending ratio of the component (C) is 0 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, further preferably 0.1 to 3 parts by weight based on 100 parts by weight of the total solid content in the composition. Parts by weight.
By blending the component (C), the adhesiveness to the plastic substrate can be improved even with a small amount of active energy ray irradiation. Moreover, transparency can be made favorable by setting it as 10 weight part or less.

4-3. Component (D) The composition of the present invention preferably contains a component (D) (organic solvent) for the purpose of obtaining a thin and smooth undercoat layer.
Although the kind of (D) component is not specifically limited, It is preferable to select the solvent which melt | dissolves (A) component and another component.

  Component (D) includes alcohols such as ethanol and isopropanol; alkylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; aromatic compounds such as toluene and xylene; propylene glycol monomethyl Examples thereof include esters such as ether acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether; and N-methylpyrrolidone.

As the component (D), the method of using the organic solvent at the time of producing the component (A) as the component (D) of the composition is preferable because it can reduce the production cost.
(D) As a ratio of a component, 10 to 99 weight% is preferable in a composition, More preferably, it is 30 to 95 weight%.

4-4. Other components other than the above In addition to the components (B) to (D) described above, various compounds can be blended in the composition of the present invention depending on the purpose.
For the purpose of adjusting the viscosity of the composition and the physical properties of the cured product, a compound having one ethylenically unsaturated group (hereinafter referred to as a monofunctional unsaturated compound) can be blended.
In the monofunctional unsaturated compound, examples of the ethylenically unsaturated group include a (meth) acryloyl group, a maleimide group, an amide group, and a vinyl group, and a (meth) acryloyl group is preferable.
Specific examples of the monofunctional unsaturated compound include (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, methyl ( Of (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, alkylphenol Alkylene oxide adduct (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Pyr (meth) acrylate, 4-hydroxybutyl acrylate, (meth) acrylate of alkylene oxide adduct of paracumylphenol, orthophenylphenol (meth) acrylate, (meth) acrylate of orthophenylphenol alkylene oxide adduct, tetrahydrofur Furyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, N- (2-hydroxyethyl) citraconimide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam and the like can be mentioned. The

  An organic polymer can also be blended with the composition of the present invention for the purpose of reducing the curing shrinkage with an inexpensive component. Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, and the like. Is mentioned.

To the composition of the present invention, a radical polymerization inhibitor or an antioxidant may be added for the purpose of enhancing storage stability and thermal stability.
Specific examples of the radical polymerization inhibitor include the compounds shown in the production of the component (A).
Specific examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate). Hindered phenolic antioxidants. Further, a sulfur-based secondary antioxidant such as 4,6-bis (octylthiomethyl) -O-cresol, a phosphorus-based secondary antioxidant, or the like may be used in combination.

  A leveling agent may be added to the composition of the present invention for the purpose of enhancing leveling properties during coating. As the leveling agent, various substances such as a silicone polymer and a fluorine atom-containing polymer can be used.

  In the composition of the present invention, an ultraviolet absorber or a light stabilizer can be blended for the purpose of enhancing UV resistance and weather resistance. Specific examples of suitable UV absorbers include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). ) -1,3,5-triazine and other hydroxyphenyl triazine ultraviolet absorbers, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, etc. Benzotriazole ultraviolet absorbers, inorganic fine particles that absorb ultraviolet rays, such as titanium oxide fine particles and zinc oxide fine particles. Specific examples of suitable light stabilizers include hindered amine light stabilizers such as bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.

  When the layer formed on the undercoat layer is an inorganic substance, the composition of the present invention is blended with a silane coupling agent or a (meth) acrylate having a phosphate group for the purpose of improving the adhesion to the inorganic substance. May be. In addition to these, various fillers such as silica and alumina, metal fine particles, pigments and the like may be blended as necessary.

5). Manufacturing method of undercoat layer The active energy ray-curable undercoat composition of the present invention may be used according to a conventional method.
Specifically, a method of irradiating active energy rays after applying the composition to the substrate can be mentioned.

  When the composition contains the component (D) (organic solvent), it is preferable that the composition is coated on a substrate, heated and dried, and then cured by irradiation with active energy rays.

As a base material, what is necessary is just to select a various base material according to the objective and use, and a metal, glass, a plastics, etc. are mentioned.
The composition of the present invention is preferably a plastic material.
Specific examples include polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyolefins such as polycarbonate, polyethylene, polypropylene and cycloolefin polymers; (meth) acrylic resins such as acrylic resins and methacrylic resins; methyl methacrylate-styrene copolymer resins (MS Resin) and polystyrene resins such as polystyrene; polyvinyl chloride; polyvinyl alcohol; triacetyl cellulose; polyether sulfone; polyamide; polyimide; urea melamine resin;
Of these, the compositions of the present invention are particularly useful for cycloolefin polymers.
When the base material is a hardly adhesive material such as polyolefin, it is preferable to carry out a surface treatment such as corona treatment or plasma treatment.

The coating method may be a conventional method, and examples thereof include bar coating, roll coating, spin coating, dip coating, gravure coating, flow coating, knife coating, die coating, cap coating, and spray coating.
What is necessary is just to set as a film thickness of the composition with respect to a base material according to the objective and a use, and the thickness from which the hardened | cured material of a composition becomes 0.1-20 micrometers is preferable, More preferably, it is 1-10 micrometers.

Specific examples of the active energy ray include an electron beam, ultraviolet rays, and visible light, and ultraviolet rays are particularly preferable.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED.
The irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm ² is preferable, and 500 to 3,000 mJ / cm ² is more preferable.

6). Laminate The composition of the present invention is used for the purpose of forming an undercoat layer on various substrates and improving the adhesion between the substrate and another organic layer or inorganic layer.
The composition of the present invention can be preferably applied to the production of a laminate having a cured film of the composition of the present invention on a substrate and further having an organic layer or an inorganic layer on the cured film.

Examples of the substrate include the same materials as described above, and a plastic substrate is preferable.
As described above, a cycloolefin polymer is preferable as the plastic substrate.

  Examples of the organic layer or the inorganic layer include a hard coat layer used for the purpose of protecting the surface of a plastic, an optical functional layer such as a lens, a polarizing plate, and a light diffusing material.

As a material for forming the hard coat layer (hereinafter referred to as “hard coat agent”), various materials can be used as long as they can be used for protecting and modifying the surface of the plastic.
Examples of the hard coat agent include organic materials, organic / inorganic hybrid materials, and inorganic materials.
Examples of the resin constituting the organic hard coat agent include melamine resin, urethane resin, alkyd resin, fluororesin, and organosilicone. Moreover, the active energy ray hardening-type composition containing the compound which has an ethylenically unsaturated group, or / and a photocationic polymerizable compound, a thermosetting composition, etc. are mentioned.
Examples of the organic / inorganic hybrid hard coat agent include those containing inorganic oxide fine particles such as silica in the organic hard coat agent described above.
Examples of the inorganic hard coat agent include a metal or metal oxide formed by a dry process such as vacuum steaming or sputtering, or a metal alkoxysilane formed by a sol-gel reaction. Examples using the sol-gel reaction include those containing ultrafine particles of metal oxide such as colloidal silica in the solution.

The cured film of the composition of the present invention is particularly excellent in adhesion with the active energy ray-curable hard coat agent, and does not impair the scratch resistance of the hard coat agent cured film. Therefore, the composition of the present invention is particularly effective as an undercoat layer as an undercoat layer of an active energy ray-curable hard coat agent composition.
That is, as a laminate produced from the composition of the present invention, a plastic substrate / cured film of the composition (undercoat layer) / cured film layer of the active energy ray-curable hard coat agent composition are formed in this order. A laminated body is preferable.
As the active energy ray-curable hard coat agent composition, the aforementioned component (B) [compound other than component (A) having two or more ethylenically unsaturated groups] and component (C) (photopolymerization initiator) The thing containing is preferable. The active energy ray-curable hard coat agent includes the component (B) and the component (C), component (D) (organic solvent), monofunctional unsaturated compound, and (a2) (inorganic oxide fine particles). ) May be included. Moreover, the photocationic composition containing a photocationic polymerizable compound may be sufficient. Examples of the cationic photopolymerizable compound include epoxy compounds and oxetane compounds.

The laminate may be produced by a conventional method. For example, the active energy ray-curable hard coat agent composition is applied to a substrate having an undercoat layer produced from the composition of the present invention. In the case where the composition contains an organic solvent, there may be mentioned a method of heating and drying and then irradiating with active energy rays to cure.
The coating conditions and heat-drying conditions in this case may follow conventional methods. The active energy ray irradiation may be performed according to the preferable conditions described above.

7). Applications The active energy ray-curable undercoat composition of the present invention and a laminate using the composition can be used for various applications.
Specifically, optical sheets and full-surface boards used for liquid crystal displays and touch panels, casings for electrical equipment such as mobile and home appliances, recording media such as optical disks, eyeglass lenses, goggles, front plates for motorcycle helmets, etc. It can be suitably used as a building material such as a plastic product, a heat ray reflective film, and a decorative board related to the field of view.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited by these Examples.
In the following, “part” means part by weight, and “%” means% by weight.

Synthesis Example 1 (Production of Maleimide Alkoxysilane [Component (a1)])
A 1 L separable flask equipped with a stirrer was charged with 266.4 g of toluene, 89.6 g (0.80 mol) of citraconic anhydride and 0.19 g of hydroquinone monomethyl ether (hereinafter also referred to as MQ), and stirred at room temperature. 176.8 g (0.80 mol) of 3-aminopropyltriethoxysilane was added dropwise. After completion of the dropwise addition, the temperature was raised until ethanol was distilled off, and then the reaction was allowed to react for 4 hours while maintaining the reaction solution in the range of 100 to 105 ° C. After completion of the reaction, low-boiling components such as toluene and ethanol were distilled off under reduced pressure while heating the flask in an oil bath at 80 ° C. to synthesize maleimide alkoxysilane (a1).
From the ¹ H-NMR spectrum, the structure of the obtained (a1) has the following formulas (1) and (2): R ¹ is a methyl group, R ² is a hydrogen atom, R is a trimethylene group, R ³ Was an ethyl group, a = 0 and z was confirmed to be 1. In addition, it is a mixture of a component having a high molecular weight by condensation by gel permeation chromatography (hereinafter referred to as “GPC”) (solvent: tetrahydrofuran) and a low molecular weight component having a small degree of condensation or not condensed. Was confirmed.

Synthesis Example 2 (Production of maleimide-silica [component (A)])
In a 500 mL separable flask equipped with a stirrer and a condenser, 37.5 g of maleimide alkoxysilane obtained in Synthesis Example 1, 120 g of propylene glycol monomethyl ether (hereinafter referred to as “PGM”), 0.01 g of MQ, and After 5.4 g of water was charged and stirred and dissolved at room temperature, colloidal silica [Nissan Chemical Co., Ltd. colloidal silica IPA-ST, average particle size: 10 to 15 nm (value measured by BET method), solid content 30%, 100 g of isopropyl alcohol] was charged. After reacting this reaction solution at 80 ° C. for 4 hours, isopropyl alcohol, water and the like were distilled off until the nonvolatile content was about 50%. Next, 100 g of PGM was added, and the operation of distilling together with water remaining in the reaction system to make the nonvolatile content 50% was repeated three times to distill off the water in the reaction system. The ingredients were synthesized.
The non-volatile content of the solution after the reaction was 59%. ^{From the 1} H-NMR spectrum, it was confirmed that no decomposition reaction such as hydrolysis of the maleimide ring occurred. From GPC, it was confirmed that the peaks of polystyrene-equivalent number average molecular weights 332 and 594 in (a1) disappeared.
Hereinafter, in the solution after completion of the reaction obtained here, the component excluding the solvent is referred to as component (A) and is referred to as “maleimide silica-1”.
For analysis, the reaction product (A) is added to 80 times by weight of acetonitrile to agglomerate and precipitate silica, then centrifuged, decanted, washed with acetonitrile, and centrifuged, and the precipitate is dried at 80 ° C. for 30 minutes. I let you. As a result of measuring the infrared absorption spectrum of the precipitate, a peak derived from the maleimide group was clearly observed together with the silica peak, and the surface modification of the colloidal silica by the maleimide group was confirmed. Moreover, as a result of estimating the organic content of this silica component by thermogravimetric analysis from room temperature to 1000 ° C., the organic content was 11%.

Synthesis Example 3 (Production of HDI3-HBA [component (B))
Into a 3 L separable flask equipped with a stirrer and an air blowing tube, an isocyanate compound having a nurate trimer of hexamethylene diisocyanate as a main component [Duranate TPA-100 manufactured by Asahi Kasei Chemicals Corporation. NCO content 23%. ] 1369.5 g (NCO 7.5 mol), 2,6-di-tert-butyl-4-methylphenol (hereinafter referred to as “BHT”) 1.22 g, dibutyltin dilaurate (hereinafter referred to as “DBTL”) 0.73 g Was added dropwise, while stirring at a liquid temperature of 50 to 70 ° C., 1080 g (7.5 mol) of 4-hydroxybutyl acrylate (hereinafter referred to as “HBA”) was added dropwise.
After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 4 hours, and the reaction was terminated by confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product. The reaction product had three (meth) acryloyl groups. A urethane (meth) acrylate compound was obtained. Hereinafter, this reaction product is referred to as “HDI3-HBA”.

Synthesis Example 4 (Production of IPDI-M305 [component (B))
To a 2 L separable flask equipped with a stirrer and an air blowing tube, triethyl and tetraacrylate of pentaerythritol [Aronix M-305 manufactured by Toagosei Co., Ltd. Hereinafter referred to as M-305. 993 g (containing 2 moles of triacrylate), 0.61 g of BHT and 0.36 g of DBTL were charged, and 222 g (1 of IPDI) of isophorone diisocyanate (hereinafter referred to as “IPDI”) was stirred at a liquid temperature of 70 to 75 ° C. 0.0 mol) was added dropwise.
After completion of the dropwise addition, the mixture was stirred at 85 ° C. for 2 hours, and the reaction was terminated by confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product, thereby obtaining a polyfunctional urethane acrylate.
Hereinafter, this reaction product is referred to as “IPDI-M305”.

● Production Example 1 (Production of active energy ray-curable hard coat composition)
In a stainless steel container, 100 g of IPDI-M305, 150 g of PGM, 5 g of 1-hydroxy-cyclohexyl-phenyl-ketone (hereinafter referred to as “HCK”), leveling agent 8019Additive (hereinafter referred to as “8019Ad” manufactured by Toray Dow Corning Co., Ltd.) The active energy ray-curable hard coat composition was manufactured by stirring and dissolving. Hereinafter, this composition is referred to as “HC-1”.

Examples 1 to 3, Comparative Example 1 and Comparative Example 2
<Manufacture of active energy ray-curable undercoat composition>
The components shown in Table 1 were stirred and dissolved by a conventional method to produce an active energy ray-curable composition. In addition, the unit of each numerical value in Table 1 is a weight part. Further, the number of PGM copies includes the amount brought in together with “maleimide silica-1”.

<Manufacturing method of undercoat layer>
After corona treatment of cycloolefin polymer (ZEONOR ZF-14, thickness 0.10 mm) manufactured by Nippon Zeon Co., Ltd., the composition shown in Table 1 was applied to a bar coater so that the coating thickness after drying was 3 μm. After coating with a hot air dryer at 80 ° C. for 2 minutes, it was cooled to room temperature and irradiated with ultraviolet rays to form an undercoat layer.
For ultraviolet irradiation, a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. was used, the lamp height was set to the focal length (10 cm) of the condenser mirror, and irradiation was performed for two passes at a conveyor speed of 10 m / min. The irradiation energy per pass was 330 mJ / cm ² in the UV-A region of UV POWER PUCK manufactured by EIT (total 660 mJ / cm ² ).
When the surface of the obtained undercoat layer was smooth, it proceeded to the manufacturing process of the laminate shown below.

<Manufacture of laminates>
On the undercoat layer, HC-1 of Production Example 1 was applied with a bar coater so that the coating thickness after drying was 7 μm, dried with a hot air dryer at 80 ° C. for 2 minutes, and then cooled to room temperature. Then, the laminate was manufactured by irradiating with ultraviolet rays and curing. The ultraviolet irradiation was performed under the same conditions as those for forming the undercoat layer.

<Evaluation method>
● Smoothness of the undercoat layer The surface of the undercoat was visually observed, and a smooth one was evaluated as “◯”, a non-smooth one was evaluated as “Δ”, and a liquid repelled as “×”.
● Adhesiveness of undercoat layer A cross-cut cellophane tape peel test was performed according to JIS-K5400, and the following evaluation was performed from the remaining area.
○: Remaining area 100%, Δ: Remaining area 90-99%, X: Remaining area less than 90%

● Hard coat wettability The surface of HC-1 was visually observed, and a smooth one was evaluated as ◯, a one recognized as non-smooth was evaluated as Δ, and a one repelled by the liquid was evaluated as ×.

-Adhesion of hard coat layer A cross-cell cellophane tape peel test was performed on HC-1 according to JIS-K5400, and the following evaluation was performed from the remaining area.
○: Remaining area 100%, Δ: Remaining area 90-99%, X: Remaining area less than 90%

Scratch resistance The HC-1 cured film was rubbed back and forth 10 times with steel wool # 0000, 300 gf / cm ² , and evaluated according to the number of scratches as follows.
○: 0 to 5, Δ: 6 to 15, ×: 16 or more

<Evaluation results>
The evaluation results are shown in Table 2. The undercoat composition of the present invention was excellent in the coating property to the substrate, and the wettability of the hardcoat composition to this cured film was also good. Further, the laminate in which the hard coat layer was formed on the undercoat layer was good in both scratch resistance and adhesion.

  The active energy ray-curable undercoat composition of the present invention can be suitably used for the production of a laminate. In particular, it can be suitably used for the production of a laminate based on a cycloolefin polymer. Further, it is particularly suitable as an undercoat for a hard coat.

Claims (13)

Active energy containing a reaction product (A) obtained by reacting an alkoxysilane compound (a1) represented by the following general formula (1) with inorganic oxide fine particles (a2) in the presence of water and an organic solvent. A composition for wire curable undercoat.
(P-SiO _3/2 ) _1-a (P-Si (R ⁰ ) O _2/2 ) _a (O _1/2 R ³ ) _z (1)

However, in the general formula (1), P represents a group represented by the following general formula (2), R ³ represents a hydrogen atom or a monovalent organic group, R ⁰ represents a monovalent organic group, a is 0 or a positive number and 0 ≦ a <1 is satisfied, z is a positive number and 0.1 ≦ z ≦ 2 is satisfied, and P, R ⁰ and R ^{3 in} one molecule are each two types The above different groups may be included, and R ⁰ and R ³ in one molecule may be the same group or different groups.
In the general formula (2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R ¹ and R ² are combined to form a 5-membered member. R represents a hydrocarbon group that forms a ring or a 6-membered ring, and R represents a divalent organic group.   The active energy ray-curable undercoat composition according to claim 1, wherein, in the general formula (2), R is a divalent saturated hydrocarbon group. 3. The active energy ray-curable undercoat composition according to claim 1, wherein in the general formula (2), ^one of R ¹ and R ² is a hydrogen atom, and the other is an alkyl group. The composition for active energy ray-curable undercoat according to any one of claims 1 to 3, wherein the compound of the general formula (1) is a compound represented by the following general formula (3).
(P′—SiO _3/2 ) (O _1/2 R ³ ′) _z (3)
However, in the general formula (3), P 'represents a group represented by the following general formula (4), R ^3' represents an organic group or a hydrogen atom monovalent C1-8, z is positive And 0.1 ≦ z ≦ 2.
In the general formula (4), one of R ⁴ and R ⁵ is a hydrogen atom and the other is an alkyl group having 1 to 6 carbon atoms, or both are alkyl groups having 1 to 6 carbon atoms, or It represents that it is a saturated hydrocarbon group that forms a 6-membered ring, and R ⁶ represents a divalent saturated hydrocarbon group having 2 to ⁶ carbon atoms.   The composition for active energy ray-curable undercoat according to any one of claims 1 to 4, wherein the inorganic oxide fine particles (a2) are colloidal silica having an average particle diameter of 1 to 200 nm.   The composition for active energy ray-curable undercoat according to any one of claims 1 to 5, further comprising a compound (B) other than the component (A) having two or more ethylenically unsaturated groups. object.   The composition for active energy ray-curable undercoat according to claim 6, wherein the component (B) contains a urethane (meth) acrylate having 3 or more (meth) acryloyl groups.   Furthermore, the composition for active energy ray hardening-type undercoats of any one of Claims 1-7 containing a photoinitiator (C).   The composition for active energy ray-curable undercoat according to claim 8, wherein the component (C) contains a thioxanthone photopolymerization initiator or a benzophenone photopolymerization initiator.   Furthermore, the composition for active energy ray hardening type undercoats of any one of Claims 1-9 containing an organic solvent (D).   A laminate comprising a plastic substrate, a cured film of the active energy ray-curable undercoat composition according to any one of claims 1 to 10, and an organic layer or an inorganic layer formed in this order.   The laminate according to claim 11, wherein the plastic substrate is a cycloolefin polymer.   The laminate according to claim 11 or 12, wherein the organic layer is a cured film of an active energy ray curable composition.