JPWO2009054508A1 - Curable composition containing a condensate of alkoxysilane - Google Patents

Abstract

[PROBLEMS] A curable composition that is excellent in smoothness when applied to a plastic substrate and dried, is less likely to warp after curing and chips when cut, and has excellent scratch resistance, transparency, adhesion, and UV resistance. To provide things. A curable composition comprising a condensate of alkoxysilane containing a structural unit represented by formula (1). [(P-SiO3 / 2) 1-a (P-Si (R0) O2 / 2) a] x (Q-SiO3 / 2) y (O1 / 2R3) z (1) P is the formula (2 Q represents an alkyl group, aryl group, aralkyl group, alkenyl group or hydrogen atom, R3 represents a hydrogen atom or a monovalent organic group, R0 represents an alkyl group, and x + y = Satisfying the conditions of 1, 0.3 ≦ x ≦ 1, 0 ≦ y ≦ 0.7, 0 ≦ z ≦ 2 and 0 ≦ a ≦ 1, and R1 and R2 each independently represent a monovalent organic group or R1 and R2 may combine to form a 5- to 6-membered ring, and R represents a divalent organic group. [Chemical 1]

Description

  The present invention relates to a curable composition containing a condensate of alkoxysilane. The curable composition of the present invention can be preferably used as an active energy ray curable composition, can be preferably used for hard coat applications, and relates to these technical fields.

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. Plastic films with excellent transparency, heat resistance and mechanical properties are also used for optical films and plates (hereinafter also abbreviated as "optical sheets") used in recent growth fields such as liquid crystal displays and projection televisions. Yes.
However, since the plastic material has a defect that the surface is easily damaged, if this defect becomes a problem in use or manufacturing process, a hard coat treatment for protecting the plastic surface is required.

  As a hard coat material, an active energy ray-curable composition is widely used because it not only excels in performance such as scratch resistance, but also saves energy, is fast curable, and is excellent in productivity. As the active energy ray-curable composition, an acrylic composition mainly composed of a polyfunctional (meth) acrylate is mainstream, and is characterized by being inexpensive and excellent in scratch resistance.

However, the polyfunctional (meth) acrylate has a problem of warpage due to a large cure shrinkage rate and a problem that chips are generated during sheet cutting.
In particular, chips are not preferable in the production site of optical sheets that require a cleanliness. In addition, when used outdoors, there is a problem that cracks are likely to occur on the surface due to exposure to ultraviolet rays (UV), and this problem is an obstacle to replacing glass with plastic in the field of automobiles and building materials. one of.

Condensation reaction of ethylenically unsaturated compound (A) having isocyanurate skeleton, inorganic fine particles (b1) and hydrolysis product of organic silane compound (b2) as a technique to reduce warpage while having excellent scratch resistance An active energy ray-curable composition comprising organic coated inorganic fine particles (B), a photopolymerization initiator (C) and a solvent (D) obtained in this manner has been reported (Patent Document 1).
Moreover, as a technique for satisfying both scratch resistance and weather resistance, (A) a resin having an alkoxysilyl group and a (meth) acryloyl group, (B) colloidal silica having a primary particle diameter of 1 to 200 nm, (C An active energy ray-curable composition containing an ultraviolet absorber and / or (D) a light stabilizer has been reported (Patent Document 2).

  Recently, a composition containing no inorganic fine particles, having excellent scratch resistance, and having a small warpage, a dipentaerythritol penta- and / or hexaacrylate, and a penta-erythritol 3- to 7-mer acrylate In addition, an active energy ray-curable composition containing a plurality of pentaerythritol acrylates in a predetermined ratio and further containing a photopolymerization initiator and a polyether-modified organopolysiloxane has been reported (Patent Document 3).

  By the way, when an active energy ray is light, as a general problem of a photocurable composition, there is a problem such as an odor derived from a decomposition product of a photopolymerization initiator. As a technique for solving this problem, polyfunctional maleimide compounds have been reported that do not require the incorporation of a photopolymerization initiator or can be photocured with a small amount of blending (Patent Documents 4 and 5).

JP 2006-225434 A JP 2004-346228 A JP 2007-231138 A Japanese Patent Laid-Open No. 11-124403 Japanese Patent Laid-Open No. 2005-23101

The compositions described in Patent Documents 1 and 2 are insufficient in terms of warpage after curing and chips at the time of cutting.
Further, the composition described in Patent Document 3 is not sufficient in terms of reduction of warpage after curing and UV resistance.
Moreover, in the compositions described in Patent Documents 4 and 5, the scratch resistance of the cured product was not sufficient.
In view of these, while having good scratch resistance, warping after curing and chips at the time of cutting are further smaller, composition excellent in UV resistance, substrate adhesion, etc., and suitable for its use A compound was desired. Particularly in the use of hard coat, a composition excellent in these performances has been desired.

  The object of the present invention is excellent in smoothness when applied to a plastic substrate and dried, hardly warps after curing and chips when cut, and excellent in scratch resistance, transparency, adhesion and UV resistance. It is to provide a curable composition, and further to provide an active energy ray-curable composition that can be cured without using a photopolymerization initiator.

  As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a maleimide group, which is an alkoxysilane condensate having a specific structure, has very excellent performance, The present invention has been completed.

  According to the present invention, it is excellent in smoothness when applied to a plastic substrate and dried, is less likely to warp after curing and chips when cut, and is excellent in scratch resistance, transparency, adhesion and UV resistance. A curable composition can be provided.

The present invention relates to a curable composition (hereinafter referred to simply as “condensate (A)”) containing a condensate (A) of alkoxysilane containing a structural unit represented by the following general formula (1). Simply referred to as “composition”).
In addition, when the composition of the present invention is used as an active energy ray-curable composition, it can be cured without using a photopolymerization initiator, and therefore problems such as odor derived from the decomposition product of the photopolymerization initiator. Can also be solved.
The composition of the present invention is excellent in smoothness when applied to a plastic substrate and dried, is less likely to warp after curing and chips when cut, and has excellent scratch resistance, transparency, adhesion and UV resistance. Since it is an excellent curable composition, it can be suitably used for various applications and can be particularly suitably used for hard coat applications.
Hereinafter, the condensate (A) will be described in detail.
In the present specification, an acryloyl group or a methacryloyl group is also expressed as a (meth) acryloyl group, and an acrylate or methacrylate is also expressed as a (meth) acrylate.

1. Condensate (A)
The alkoxysilane condensate (A), which is the main component of the composition of the present invention, is a compound containing a structural unit represented by the following general formula (1).
[(P—SiO _3/2 ) _1-a (P—Si (R ⁰ ) O _2/2 ) _a ] _x (Q—SiO _3/2 ) _y (O _1/2 R ³ ) _z. 1)

However, in the general formula (1), P represents a group represented by the following general formula (2), Q represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group or a hydrogen atom, R ³ is a hydrogen atom or R ¹ represents a monovalent organic group, R ⁰ represents an alkyl group having 1 to 6 carbon atoms, x represents a positive number, y, z and a represent 0 or a positive number, x + y = 1, 0. Satisfying the conditions of 3 ≦ x ≦ 1, 0 ≦ y ≦ 0.7, 0 ≦ z ≦ 2 and 0 ≦ a ≦ 1, and P, Q, R ⁰ and R ³ in one molecule are each two or more types Different groups may be included, and Q and R ⁰ , Q and R ³ , or R ⁰ and R ³ in one molecule may be the same group or different groups. Also good.

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 group.

The condensate (A) should just contain the structural unit represented by the said General formula (1), The structure is arbitrary, A linear, basket shape, ladder shape, and cyclic | annular form may be sufficient.
Hereinafter, P, Q, R ³ , R ⁰ , x, y, z, and a in the general formula (1) will be described.

In the general formula (1), P is a group represented by the general formula (2).
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.
Furthermore, as R ¹ and R ² , both are hydrogen atoms, or one is a hydrogen atom and the other is an alkyl group, so that the curability of the composition is excellent and the cured product is excellent in scratch resistance. More preferable in terms.
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. Preferable examples include an alkylene group, —R ⁸ —OCONH—R ⁹ —, —R ¹⁰ —S—R ⁹ —, —R ¹⁰ —NH—R ⁹ — and the like. Here, R < ⁸ > and R < ⁹ > represent a C1-C6 alkylene group. The alkylene group may be linear or branched. R ¹⁰ means a group obtained by removing a maleimide group and a thiol or amine from a compound having a maleimide group and a compound having an ethylenically unsaturated group at the terminal and a thiol or amine, specifically, an alkylene group and — R ¹¹ OCOC (R ¹² ) CH ₂ — can be mentioned. R ¹¹ represents an alkylene group having 1 to 6 carbon atoms, and R ¹² represents a hydrogen atom or a methyl group.

  R is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, and more preferably 3 to 6 carbon atoms in that the cured product of the composition has excellent scratch resistance and UV resistance. Are particularly preferred.

In General formula (1), Q is an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or a hydrogen atom.
Moreover, the alkyl group, aryl group, aralkyl group and alkenyl group in Q may have a substituent.
The substituent is not particularly limited as long as there is no problem in curability and the like, but an alkyl group, an aryl group, an aralkyl group, an alkenyl group, a (meth) acryloyl group, an amino group, an oxetanyl group, and a halogen atom Etc. can be illustrated.
In the alkyl group, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
Preferred examples of the substituent in the alkyl group include a (meth) acryloyl group, an amino group, an oxetanyl group, and a halogen atom. Specific examples of the alkyl group having a (meth) acryloyl group include a γ- (meth) acryloyloxypropyl group, and specific examples of the alkyl group having an amino group include a γ-aminopropyl group. Specific examples of the alkyl group having an oxetanyl group include (3-ethyloxetane-3-yl) methoxypropyl group and the like, and specific examples of the alkyl group having a halogen atom include trifluoropropyl group and the like. Can be mentioned.
Examples of the aryl group include a phenyl group, a p-styryl group, and a toluyl group.
Examples of the aralkyl group include a benzyl group.
Examples of the alkenyl group include a vinyl group and an allyl group.
Among these, a methyl group and a phenyl group are preferable in that the cured product of the composition is excellent in scratch resistance and UV resistance.

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 a group having a structure in which a hydroxyl group is removed from diacetone alcohol, a 2-acryloyloxyethyl group, and the like.
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), the alkyl group having 1 to 6 carbon atoms represented by R ⁰ is preferably an alkyl group having 1 to 3 carbon atoms in that the cured product of the composition has excellent scratch resistance. More preferred is a methyl group or an ethyl group.

In the general formula (1), x represents a positive number, y, z, and a represent 0 or a positive number, x + y = 1, 0.3 ≦ x ≦ 1, 0 ≦ y ≦ 0.7, 0 ≦ z ≦ 2 and 0 ≦ a ≦ 1 are satisfied.
x, y, and z are units of ((P—SiO _3/2 ) _1-a (P—Si (R ⁰ ) O _2/2 ) _a ] in the entire condensate (A), respectively (Q—SiO _3/2 ) means the average value of the unit and (O _1/2 R ³ ) unit, and a is [(P—SiO _3/2 ) _1-a (P—Si (R ⁰ ) O _2/2 ) _a ] Means the average ratio of (P-Si ( ^R0 ) O2 _{/ 2} ) units in units.
The range of x is 0.3 ≦ x ≦ 1, and preferably 0.5 ≦ x ≦ 1. It is preferable that x is 0.3 or more because the curability of the composition is excellent. The range of y is 0 ≦ y ≦ 0.7, and 0 ≦ y ≦ 0.5 is preferable. It is preferable for y to be 0.7 or less because the curability of the composition is excellent.
The range of z is 0 ≦ z ≦ 2, preferably 0 ≦ z ≦ 1.5, and more preferably 0 ≦ z ≦ 1. By setting z to 2 or less, the condensate (A) can be made to be a high molecular weight product, which is preferable because the cured product is excellent in scratch resistance.
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 the condensate (A), a compound with y = 0 and a = 0 is preferable because of excellent scratch resistance.
The values of x, y, z and a can be determined from the integration ratio of hydrogen atoms by measuring the ¹ H-NMR spectrum of the condensate (A).

P, Q, R ⁰ and R ³ in one molecule may contain two or more different groups. That is, (P—SiO _3/2 ) _1-a unit, (P—Si (R ⁰ ) O _2/2 ) _a unit, (Q—SiO _3/2 ) unit, and (O Each unit of the _1/2 R ³ ) unit 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, Q and R ⁰ , Q and R ³ , or R ⁰ and R ³ in one molecule may be the same group or different groups.

As a weight average molecular weight of a condensate (A), 500-100,000 are preferable, More preferably, it is 500-10,000.
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.

As the condensate (A), one containing a structural unit represented by the following general formula (3) and having a weight average molecular weight of 500 to 100,000 is most preferable.
(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 a monovalent organic group having 1 to 8 carbon atoms, z is 0 or a positive number And 0 ≦ z ≦ 2.

In General Formula (4), one of R ⁴ and R ⁵ represents a hydrogen atom and the other represents an alkyl group having 1 to 6 carbon atoms, and R ⁶ represents an alkylene group having 2 to ⁶ carbon atoms.

R ⁴ and R ^{5 each} represents a hydrogen atom and the other represents an alkyl group having 1 to 6 carbon atoms, and the alkyl group having 1 to 6 carbon atoms includes an alkyl group having 1 to 4 carbon atoms in the composition. It is more preferable at the point which is excellent in sclerosis | hardenability.
R ⁶ represents an alkylene group having 2 to ⁶ carbon atoms, and the alkylene group may be linear or branched. The “alkylene group” in the present invention represents an “alkanediyl group”. Examples of the linear alkylene 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. 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 alkylene group having 3 to 6 carbon atoms.

2. Production method of condensate (A) In the following description,
A maleimide group-containing trialkoxysilane represented by the general formula P—Si (OR ³ ) ₃ is converted into a maleimide group-containing dialkoxysilane represented by the compound (p-1) and the general formula P—Si (R ⁰ ) (OR ³ ) _2. The alkoxysilane is referred to as the compound (p-2), and the silane compound represented by the general formula Q-Si (OR ³ ) ₃ is referred to as the compound (q). Moreover, a compound (p-1) and a compound (p-2) are named generically, and it is called a compound (p). Note that P, Q, R ⁰ and R ³ have the same meaning as in the above formula (1).
As the condensate (A), those produced by various methods can be used.
For example, a production method in which the compound (p) is hydrolyzed / condensed, or a production method in which the compound (p) and the compound (q) are hydrolyzed / condensed (hereinafter also referred to as the production method 1), and the compound (p And a production method in which an alkoxy group is hydrolyzed / condensed (hereinafter also referred to as production method 2).
In the present invention, it is preferable to produce the condensate (A) by the production method 2 because it is not necessary to produce the compound (p) once to produce the condensate (A), which is simple and low cost. .
Hereinafter, Production Method 1 and 2 will be described.

2-1. Manufacturing method 1
In the production method 1, the compound (p) is hydrolyzed / condensed, or the compound (p) and the compound (q) are hydrolyzed / condensed.
Hereinafter, the compound (p-1), the compound (p-2) and the compound (q) which are raw material compounds will be described.

2-1-1. Compound (p-1)
The compound (p-1) may be any compound as long as it satisfies P-Si (OR ³ ) ₃ , and specifically, the production methods shown in the following [1] to [4] (hereinafter referred to as raw material production methods, respectively) The compounds obtained by [1] to [4] are preferred.

[1] Addition product of a compound having a maleimide group and an ethylenically unsaturated group other than the maleimide group and trialkoxysilane

[2] Addition reaction product of compound having maleimide group and hydroxyl group and compound having isocyanate group and trialkoxysilyl group

[3] Addition reaction product of a compound having a maleimide group and an ethylenically unsaturated group other than the maleimide group and a compound having a mercapto group and a trialkoxysilyl group

[4] Addition reaction product of compound having maleimide group and ethylenically unsaturated group other than maleimide group and compound having amino group and trialkoxysilyl group

  Hereinafter, the manufacturing method of these compounds (p-1) is demonstrated.

(1) Raw material manufacturing method [1]
In the raw material production method [1], preferred examples of the compound having a maleimide group and an ethylenically unsaturated group other than the maleimide group include a compound represented by the following formula (11).

In the formula (11), R ¹ and R ² are as defined above. R ⁷ means a group containing an ethylenically unsaturated group at the terminal.
Preferable examples of R ⁷ in the raw material production method [1] include an allyl group.
The addition reaction product of the compound represented by the formula (11) and trialkoxysilane can be produced by a method such as a hydrosilylation reaction in the presence of a platinum-based catalyst.

(2) Raw material manufacturing method [2]
In the raw material production method [2], preferred examples of the compound having a maleimide group and a hydroxyl group include a compound represented by the following formula (12).

In the formula (12), R ¹ and R ² are as defined above. R ⁸ represents an alkylene group having 1 to 6 carbon atoms. The alkylene group for R ⁸ may be linear or branched.
Preferable examples of the compound having an isocyanate group and a trialkoxysilyl group include a compound represented by the following formula (13).

In the formula (13), R ³ has the same meaning as described above. R ⁹ represents an alkylene group having 1 to 6 carbon atoms. The alkylene group for R ⁹ may be linear or branched.
The addition reaction product of the compound represented by the formula (12) and the compound represented by the formula (13) can be produced by mixing both and heating and stirring. At this time, a catalyst for urethanization reaction such as a tertiary amine compound or a tin-based catalyst may be added.

(3) Raw material manufacturing method [3]
In the raw material production method [3], as a preferable example of the compound having a maleimide group and an ethylenically unsaturated group other than the maleimide group, in the compound represented by the above formula (11), R ⁷ is (meth) acryloyl. The compound etc. which are oxyalkyl groups can be mentioned.

  Preferable examples of the compound having a mercapto group and a trialkoxysilyl group include a compound represented by the following formula (14).

In the formula (14), R ³ and R ⁹ are as defined above.
The addition reaction product of the compound represented by the formula (11) and the compound represented by the formula (14) can be produced by mixing both and heating and stirring. At this time, a catalyst such as a tetraalkylammonium salt may be added.

(4) Raw material manufacturing method [4]
In the raw material production method [4], as a preferred example of the compound having a maleimide group and an ethylenically unsaturated group other than the maleimide group, in the compound of the above formula (11), R ⁷ is a (meth) acryloyloxyalkyl group. A certain compound etc. can be mentioned.
Preferable examples of the compound having an amino group and a trialkoxysilyl group include a compound represented by the following formula (15).

In the formula (15), R ³ and R ⁹ are as defined above.
The addition reaction product of the compound represented by the formula (11) and the compound represented by the formula (15) can be produced by mixing both and heating and stirring. At this time, a catalyst such as a tetraalkylammonium salt may be added.

2-1-2. Compound (p-2)
The compound (p-2) is a compound represented by P—Si (R ⁰ ) (OR ³ ) ₂ .
Compound (p-2) in the raw material production method, in [1], trialkoxysilane is converted to alkyldialkoxysilane,
In [2], a compound having an isocyanate group and a trialkoxysilyl group is changed to a compound having an isocyanate group and an alkyldialkoxysilyl group.
In [3], a compound having a mercapto group and a trialkoxysilyl group is changed to a compound having a mercapto group and an alkyl dialkoxysilyl group.
In [4], the compound having an amino group and a trialkoxysilyl group may be replaced with a compound having an amino group and an alkyldialkoxysilyl group.

2-1-3. Compound (q)
The compound (q) is a compound represented by the general formula Q-Si (OR ³ ) ₃ .
Specific examples of Q include the same as those described above.
Specific examples of the compound (q) include the following examples.

  Specific examples of when Q is an alkyl group include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and ethyltripropoxysilane.

  Specific examples of when Q is an aryl group include phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltripropoxysilane.

  Specific examples of when Q is an aralkyl group include benzyltrimethoxysilane, benzyltriethoxysilane, and benzyltripropoxysilane.

Specific examples when Q is a (meth) acryloyloxyalkyl group include γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, and γ- (meth) acryloyloxypropyltri Examples include propoxysilane.
Specific examples of when Q is an aminoalkyl group include compounds in which the (meth) acryloyloxy group is replaced with an amino group.

  Specific examples of when Q is an alkenyl group include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltripropoxysilane.

  Specific examples of when Q is a hydrogen atom include trimethoxysilane, triethoxysilane, and tripropoxysilane.

  Among these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable.

2-1-4. Condensate (A) by Production Method 1 Production method of the condensate (A) by Production Method 1 includes the step of producing the compound (p) when producing a condensate of y = 0 in the general formula (1). ) Can be hydrolyzed and condensed.
In this case, when the compound (p-1) and the compound (p-2) are used in combination, the number of moles of the compound (p-1) and the compound (p-2) should be set according to the target value of a. It ’s fine.

In the case of producing a condensate with y ≠ 0 in the general formula (1), the compound (p) and the compound (q) can be produced by hydrolysis and condensation.
In this case, the ratio of the compound (p) and the compound (q) may be appropriately set according to the structure of the target condensate (A), but the total moles of the compound (p) and the compound (q). It is preferable to set the number of moles of compound (q) to 0 to 0.7 times the number of moles.

  As the condensate (A), plural types of compounds (p) can be hydrolyzed and condensed. For example, the method of using together the multiple types of compound (p) from which a maleimide group differs, or manufacturing together using the multiple types of the compound (p) from which an alkoxy group differs is mentioned. Also, a plurality of types of compounds (q) can be co-condensed.

A preferable method for producing the condensate (A) of the present invention includes a method of heating and stirring the compound (p) or the compound (p) and the compound (q) in the presence of water.
As a ratio of water, 1-6 mol is preferable with respect to 1 mol of compound (p) or 1 mol of compound (p) and compound (q) total amount, More preferably, it is 1.5-4 mol. . The heating temperature may be appropriately set according to the structure of the target condensate (A), but is preferably 0 to 160 ° C.

Moreover, it can also condense in presence of an acid catalyst or an alkali catalyst as needed.
Specific examples of the acid catalyst include acetic acid, sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid.
Specific examples of the alkali catalyst include potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide.

The condensation reaction is preferably performed in an organic solvent.
Examples of the organic solvent include aromatic compounds such as toluene and xylene, and alcohol solvents such as ethanol and isopropyl alcohol.
As a ratio of the organic solvent, a ratio in which the finally obtained condensate is 10 to 70% by weight is preferable.

2-2. Manufacturing method 2
Production method 2 is a production method in which an alkoxy group is hydrolyzed and condensed while the compound (p) is produced.

As production method 2, aminoalkyltrialkoxysilane and / or aminoalkyl (alkyl) dialkoxysilane is added to a carboxylic acid anhydride having a double bond to form an amic acid, followed by ring closure to form a maleimide group, A method in which water generated by the ring closure reaction is consumed in the hydrolysis reaction of the alkoxy group is preferable (hereinafter also referred to as production method (2-1)).
In the production method (2-1), after generating an amic acid or ring-closing to form a maleimide group, adding a suitable amount of water to further proceed the hydrolysis / condensation reaction can improve the scratch resistance. Is preferable from the viewpoint of obtaining an active energy ray-curable composition excellent in. On the other hand, when the viscosity of the condensate is reduced to facilitate handling, or when it is cured with moisture or heat after being applied to the substrate, it is preferable not to add water during production.

  Further, the condensate (A) obtained by the production method 2 may contain a small amount of a condensate having an amic acid structure in which a maleimide group is opened.

2-2-1. Production method of condensate of general formula (3) Hereinafter, production method (2-1) will be described. Condensate (A) represented by general formula (3), which is a preferred condensate [hereinafter, condensate] (Also referred to as (3A)) will be described on the basis of the manufacturing method.

  Examples of the carboxylic acid anhydride having a double bond include a compound represented by the following formula (16).

In the formula (16), R ¹ and R ² are as defined above.
Preferable examples of aminoalkyltrialkoxysilane include compounds represented by the following formula (17).

In the formula (17), R ³ and R ⁹ are as defined above.

The process of producing the condensate (A) by this reaction will be described using the compounds of the above formulas (16) and (17).
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, AMA closes to form compound (p-1), and at the same time, water is produced. Compound (p-1) is condensed with this generated water or water added separately in addition to this to produce a condensate (A) [Reaction Formula (2)].

  At the same time, AMA is produced by hydrolyzing and condensing an alkoxy group with water generated by the above formula (2) or separately added water, and ring-closing to produce a condensate (A) [Reaction Formula (3)] .

  It is considered that these processes mainly proceed in a complex manner to produce a condensate (A).

As a preferable method of the production method (2-1), an aminoalkyltrialkoxysilane is added to an organic solvent containing a carboxylic acid anhydride having a double bond to form an amic acid, and then heated and stirred. And dehydrating and ring-closing to obtain a maleimide group, and simultaneously hydrolyzing and condensing a part of the alkoxy group, and finally adding water and heating and stirring to increase the degree of condensation. If necessary, the solvent may be removed while heating to further increase the degree of condensation.
In the step of producing an amic acid by the reaction between a carboxylic acid anhydride having a double bond and an aminoalkyltrialkoxysilane, the reaction proceeds with heat generation, and thus there is no need for heating.

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.

2-2-2. The method for producing the condensate (3A) has been described above for the method for producing the condensate ( A) with y = 0 in the general formula (1) .
Next, a method for producing a condensate (A) where y = 0 in the general formula (1) other than the condensate (3A) will be described.
In the general formula (1), as the method for producing the condensate (A) of a = 1 and y = 0, aminoalkyltrialkoxysilane is replaced with aminoalkyl (alkyl) dialkoxysilane in the above, and the same as described above. It can be manufactured by the method and conditions.
In addition, in the general formula (1), as a method for producing the condensate (A) in which a ≠ 1 and y = 0, aminoalkyltrialkoxysilane, aminoalkyltrialkoxysilane and aminoalkyl (alkyl) disilane are used as described above. It can replace with the mixture of alkoxysilane, and can manufacture it by the same method and conditions as the above-mentioned.
In this case, the proportions of aminoalkyltrialkoxysilane and aminoalkyl (alkyl) dialkoxysilane may be appropriately set according to the target value of a.

2-2-3. Method for Producing Condensate (A) wherein y ≠ 0 in General Formula (1) When producing a condensate where y ≠ 0 in the general formula (1), the compound ( q) may be added.
Preferably, when an aminoalkyltrialkoxysilane and / or aminoalkyl (alkyl) dialkoxysilane (hereinafter also referred to as an amino group-containing alkoxysilane) is added to an organic solvent containing a carboxylic acid anhydride having a double bond. In addition, the compound (q) is added simultaneously with the addition of the amino group-containing alkoxysilane, and in the organic solvent containing the carboxylic acid anhydride having a double bond, the amino group-containing alkoxysilane is added to form an amic acid. Examples thereof include a method of adding the compound (q) after the formation.
In this case, the ratio of the compound (p) and the compound (q) may be appropriately set according to the structure of the target condensate (A), but the total moles of the compound (p) and the compound (q). It is preferable to set the number of moles of compound (q) to 0 to 0.7 times the number of moles.

2-2-4. Other Reaction Conditions In the production method, as in Production Method 1, a plurality of types of compounds (p) can be co-condensed or a plurality of types of compounds (q) can be co-condensed.

The reaction is preferably performed in an organic solvent.
As the organic solvent, those which do not react with the raw materials are preferable, and 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 are also used. be able to.
As a ratio of the organic solvent, a ratio in which the finally obtained condensate is 10 to 70% by weight is preferable.

  When water is added during the synthesis for the purpose of obtaining a curable composition having excellent scratch resistance, the ratio of water to be added is preferably 5 mol or less, more preferably 0. It is 1-3 mol, Most preferably, it is 0.3-1.5 mol. The heating temperature may be appropriately set according to the structure of the target condensate (A), but is preferably 50 to 160 ° C.

The reaction can be carried out in the presence of an acid catalyst or an alkali catalyst as necessary.
However, in the production method (2-1), the reaction proceeds sufficiently without these catalysts. The condensate (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 or (meth) acryloyl group of the raw material or product, and even if oxygen-containing gas such as air is introduced into the reaction solution. Good.
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.

2-3. Manufacturing method 3
As another method for producing the condensate (A), the amino group-containing alkoxysilane is first hydrolyzed and condensed, and then the compound represented by the formula (16) is added to the amino group of the condensate, A method of heating and ring closure (also referred to as production method 3) is also included.

2-4. Preferable method for producing condensate (A) Among these, the method for producing the condensate (A) of the present invention is a method in which an aminoalkyltrialkoxy is added to a carboxylic acid anhydride having a double bond represented by the general formula (16). Silane and / or aminoalkyl (alkyl) dialkoxysilane is added to form an amic acid, and the amic acid is cyclized to form a maleimide group, and water generated by the cyclization reaction is consumed by hydrolysis of the alkoxy group. It is preferable that it is a manufacturing method including the process to make.

In the general formula (16), 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.

3. Curable composition The present invention relates to a curable composition containing the above-mentioned condensate (A).
The composition of the present invention can be used as a thermosetting composition or an active energy ray curable composition.

  Since the condensate (A) has a maleimide group, it does not contain a photopolymerization initiator by irradiation with an active energy ray, or has a small curability, and has excellent curability. It can be suitably used as an active energy ray-curable composition.

Various compounds can be blended in the composition of the present invention according to the purpose.
Specific examples thereof include compounds other than the component (A) having a total of two or more (meth) acryloyl groups and / or maleimide groups in one molecule.
Examples of such compounds include compounds having two or more (meth) acryloyl groups (hereinafter also referred to as polyfunctional (meth) acrylates), compounds having two or more maleimide groups (hereinafter also referred to as polyfunctional maleimide compounds). And a compound having one or more (meth) acryloyl groups and one or more maleimide groups (hereinafter also referred to as maleimide (meth) acrylate).
The total number of (meth) acryloyl groups and maleimide groups in the compound other than the component (A) having 2 or more (meth) acryloyl groups and / or maleimide groups in total in the molecule is 2 to 10. It is preferable that the number is 3 to 10, more 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, 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) a Relate, 1,9-nonanediol di (meth) acrylate, 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 alkylene oxide adduct tri- and tetraacrylate, isocyanuric acid alkylene oxide adduct triacrylate, ε-caprolactone-modified tris ((meth) acryloxyethyl) Isocyanurate), ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa and pentaacrylate, polyester (meth) Examples thereof include 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 phenol or cresol novolac type epoxy resin, (meth) acrylic acid of diglycidyl ether of polyether Additives, (meth) acrylic acid adducts of polybutadiene diglycidyl ether, (meth) acrylic acid adducts of polybutadiene internal epoxidized products, (meth) acrylic acid adducts of silicone resins with epoxy groups, alicyclic epoxy resins (Meth) acrylic acid adducts and the like.

Examples of the urethane (meth) acrylate include compounds obtained by addition reaction of organic polyisocyanate and hydroxyl group-containing (meth) acrylate, and compounds obtained by addition reaction of organic polyisocyanate, polyol and hydroxyl group-containing (meth) acrylate.
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, and 3-methyl-1,5-pentanediol.
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 include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, pentaerythritol tri ( Examples thereof include hydroxyl group-containing polyfunctional (meth) acrylates such as (meth) acrylate, di (meth) acrylate of an isocyanuric acid alkylene oxide 3-mol adduct, and dipentaerythritol pentaacrylate.

  Among polyfunctional (meth) acrylates, when the composition is used for hard coat applications, a compound having three or more (meth) acryloyl groups is preferable because of excellent scratch resistance. More preferable examples include dipentaerythritol hexa and pentaacrylate, triacrylate of alkylene oxide 3 mol adduct of isocyanuric acid, tri and tetraacrylate of pentaerythritol, and the like.

As the polyfunctional maleimide compound, various compounds can be used as long as they have a maleimide group other than the condensate (A). In this case, the maleimide group is preferably the same group as the maleimide group in the formula (1).
Examples of the compound having a polyfunctional maleimide group include urethane compounds obtained by adding N- (2-hydroxyethyl) citraconimide to isophorone diisocyanate, diols such as N- (2-hydroxyethyl) citraconimide and polyester diol, and isophorone. Examples include urethane compounds obtained by addition reaction with diisocyanate and MIA-200 manufactured by Dainippon Ink Co., Ltd., which is a compound having two maleimide groups.

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

  In the composition of the present invention, a compound having one unsaturated group in one molecule is added for the purpose of reducing the viscosity when used in the absence of a solvent or for the purpose of increasing the adhesion to the adherend. May be.

  As the unsaturated group, a (meth) acryloyl group, a maleimide group, an amide group and a vinyl group are preferable.

  Specific examples include (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, methyl (meth) acrylate, ethyl ( (Meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate of alkylene oxide adduct of phenol, alkylene oxide adduct of alkylphenol ( (Meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acryl , 4-hydroxybutyl acrylate, (meth) acrylate of alkylene oxide adduct of paracumylphenol, orthophenylphenol (meth) acrylate, (meth) acrylate of alkylene oxide adduct of orthophenylphenol, tetrahydrofurfuryl (meta ) 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.

The composition of the present invention contains an organic solvent (hereinafter simply referred to as a solvent) when it is coated with a thin film such as a hard coat or when the condensate (A) has a high degree of condensation and a high viscosity. It is preferable.
Although the kind of solvent is not specifically limited, It is preferable to select the solvent which melt | dissolves (A) component and another component.

Solvents include 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 ether acetate; Examples thereof include esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether; and N-methylpyrrolidone.
When a hydroxyl group-containing compound such as alcohol, alkylene glycol monoether and acetone alcohol is used as the solvent, a part of the R ³ alkoxy group in the condensate (A) may be substituted with the hydroxyl group-containing compound. It is possible to use.

As the solvent, the method of using the solvent during the production of the component (A) as it is as the solvent of the composition is preferable because it can reduce the production cost. In addition, when the substrate to which the composition is applied is a material in which a trace amount of solvent such as wood tends to remain, it is also preferable to remove the solvent during synthesis and replace it with a highly safe solvent such as ethanol.
However, in the composition of the present invention, a solvent is not essential, and when the condensation degree of the condensate (A) is not high and the viscosity is not too high and / or when diluted with a low viscosity monomer, a solventless system is used. It can also be a composition.

  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 methacrylate, cyclohexyl (meth) acrylate, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, and the like. .

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 phenolic compounds such as hydroquinone and hydroquinone monomethyl ether.
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.

In addition to this, various fillers such as silica and alumina, fine metal particles, pigments, and the like may be blended with the composition of the present invention as necessary.
In the present invention, “fine particles” are preferably particles having an average particle diameter of 1 to 100 nm.

  When the composition of the present invention is thermally cured, it is preferable to incorporate a thermal radical polymerization initiator such as an organic peroxide or an azo compound.

  In the composition of the present invention, various catalysts can be blended in order to accelerate the hydrolysis / condensation reaction of the remaining alkoxysilane after coating. Examples of the catalyst include acids, bases, acid generators such as thermal cationic polymerization initiators and photocationic polymerization initiators, photobase generators, and metal alkoxides and metal complexes containing metals such as Al, Ti and Sn. It is done.

4). Active energy ray-curable composition As described above, the composition of the present invention can be preferably used as an active energy ray-curable composition.

In this case, a photosensitizer or a photopolymerization initiator may be added for the purpose of increasing the curing rate or increasing the adhesion to the substrate.
Suitable photosensitizers include thioxanthone compounds such as diethyl thioxanthone and diisopropyl thioxanthone, acetophenone, and benzophenone.

When the composition of the present invention is used as an active energy ray-curable composition, as described above, it can be cured without adding a photopolymerization initiator, but for the purpose of increasing the curing rate, etc. An initiator can also be added.
Specific examples of the photopolymerization initiator 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 compounds such as phenyl} -2-methyl-propan-1-one; benzophenones such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4′-methyl-diphenylsulfide Α-ketoester compounds such as methylbenzoylformate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine Phosphine oxide compounds such as oxides; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) phenyl] Acetophenone / benzophenone hybrid photoinitiators such as 2-methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1 Oxime ester-based photopolymerization initiators such as 2-octanedione; and camphorquinone.

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.

5. Applications The composition of the present invention can be used for various applications. For example, a coating agent, an adhesive agent, etc. can be mentioned.
In addition to these uses, the active energy ray-curable composition can be used for cladding materials for optical waveguides, insulating coating materials for electrical wiring, and photoresists.
The applicable base material can be used for various materials, and examples thereof include polymers such as plastic, glass, metal, ceramics, vapor-deposited film of metal oxide, silicon, and wood.

  The composition of the present invention can be preferably used as a coating agent, and can be suitably used for a hard coat of a polymer material, a paint for woodwork, and the like.

  Specific examples of the polymer include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, cycloolefin polymer, acrylic resin, methacrylic resin, methyl methacrylate-styrene copolymer resin (MS resin), polystyrene, and polyvinyl chloride. , Polyvinyl alcohol, triacetyl cellulose, polyethersulfone, polyamide, polyimide, urea / melamine resin, epoxy resin, polyurethane, polylactic acid, liquid crystal polymer, and the like. When the polymer is difficult to adhere, it is preferable to perform easy adhesion treatment such as corona treatment in order to improve adhesion.

  When using the composition of this invention for a hard coat, you may mix | blend metal alkoxides, such as tetraethoxysilane, in order to further improve the abrasion resistance of hardened | cured material. Here, in order to make hydrolysis reaction effective, you may mix | blend a photo-acid generator and a photobase generator.

  In order to further improve the scratch resistance of the cured product, inorganic fine particles such as colloidal silica may be blended. As the colloidal silica, colloidal silica having a particle diameter of several nanometers to several tens of nanometers and uniformly dispersed in an organic solvent is preferable. Here, the surface of the colloidal silica may be modified by adding a silane coupling agent having a (meth) acryloyl group and an alkoxysilyl group to the surface of the colloidal silica.

The most preferred use form of the composition of the present invention is an active energy ray-curable hard coat composition.
In this case, a composition containing a solvent is preferable for the purpose of improving coatability.
Specific examples of the solvent are as described in the section of the curable composition.
As a ratio of the solvent in a composition, 30 to 90 weight% is preferable.

As a method for producing the hard coat, a conventional method may be used. For example, a method of applying a composition to a substrate and drying it by heating, followed by irradiating with active energy rays and curing may be mentioned.
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.

  Active energy ray curable hard coat compositions are hard coats for optical sheets used in liquid crystal displays and projection televisions, and hard coats for plastic products related to the field of view, such as eyeglass lenses, goggles, and front panels of motorcycle helmets. Can be suitably used. Moreover, it can be suitably used as a hard coat on a housing of a mobile product such as a mobile phone or a home appliance. Furthermore, it can be suitably used as a hard coat of glass substitute plastic. Specifically, it can be suitably used as a hard coat in the case of replacing glass parts of automobiles and trains, glass parts of building materials and furniture with plastics.

  For base materials other than plastics, it can be used for various applications such as hard coatings for wooden floors and paints for vehicle exteriors such as automobiles, bicycles and trains.

When the composition of the present invention is used as a coating agent, the present invention also relates to an article formed by forming a cured film of the composition of the present invention on the surface of a substrate.
Specific examples and preferred examples of the substrate in this case include the same ones as described above.
As a method for forming a cured film, a conventional method may be followed. After applying the composition to a substrate, it is heated in the case of a thermosetting composition, and in the case of an active energy ray curable composition, it is active. Examples include a method of irradiating energy rays.
In this case, the composition coating method, heating conditions, active energy ray irradiation conditions, and the like may be in accordance with conventional methods.

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.

(Example 1 [Production of condensate (3A)])
A 500 ml separable flask equipped with a stirrer and a condenser tube was charged with 100 g of toluene, 33.6 g (0.30 mol) of citraconic anhydride and 0.067 g of hydroquinone monomethyl ether (hereinafter also referred to as MQ) while stirring at room temperature. , 66.3 g (0.30 mol) of γ-aminopropyltriethoxysilane was added dropwise.
This was stirred at 50 ° C. for 1 hour, then refluxed for 4 hours with heating and stirring in a 125 ° C. oil bath, and then allowed to stand overnight at room temperature.
Next, 2.7 g (0.15 mol) of water was added, and the mixture was stirred at 50 ° C. for 1 hour, further stirred at 75 ° C. for 1 hour, and then heated and stirred in a 115 ° C. oil bath to distill off distilled ethanol and the like. The reaction was carried out at normal pressure for 4 hours. Finally, in order to completely distill off toluene, ethanol, etc., the mixture was stirred under reduced pressure at 80 ° C. and 80 Torr for 1 hour, and then stirred under reduced pressure at 80 ° C. and 10 Torr for 1 hour to obtain a highly viscous liquid product (condensate (3A )).
¹ H-NMR spectrum of the obtained condensate (3A) was measured. The result is shown in FIG. From FIG. 1, it was confirmed that the obtained condensate (3A) was an alkoxysilane condensate having a citraconimide group. The condensate (3A) is a compound in which R ⁴ is a methyl group, R ⁵ is a hydrogen atom, R ⁶ is a propylene group, R ³ is an ethyl group, and z is 0.6 in formula (3).
Further, as a result of measuring the obtained condensate (3A) by gel permeation chromatography (hereinafter also referred to as GPC) (solvent: tetrahydrofuran), the weight average molecular weight (hereinafter also referred to as Mw) in terms of polystyrene was 4,600. Met.
Hereinafter, this product is referred to as CS-1.

(Example 2 [Production of condensate (A)])
Into a flask similar to that in Example 1, 131 g of toluene, 33.6 g (0.30 mol) of citraconic anhydride and 0.074 g of MQ were charged, and 66.3 g (0.30 mol) of γ-aminopropyltriethoxysilane was stirred at room temperature. ) And 31.2 g (0.13 mol) of phenyltriethoxysilane were added dropwise.
This was stirred at 50 ° C. for 1 hour, then refluxed for 4 hours with heating and stirring in a 125 ° C. oil bath, and then allowed to stand overnight at room temperature.
Next, 6.3 g (0.35 mol) of water was added, and the mixture was refluxed for 5 hours with stirring in an oil bath at 115 ° C. to obtain a toluene-ethanol mixed solvent solution of the condensate (A).
As a result of removing a small amount of the obtained solution and removing the solvent and measuring the ¹ H-NMR spectrum of the condensate (A), R ¹ is a methyl group and R ² is a hydrogen atom in formula (1) and formula (2). , R is a propylene group, Q is a phenyl group, R ³ is an ethyl group, x is 0.7, y is 0.3, z is 0.4, and a is 0.
Moreover, as a result of GPC measurement of the obtained condensate (A) by the same method as Example 1, Mw was 1,030.
Hereinafter, the condensate (A) obtained here is referred to as CPS-1.
This product was a solution containing 32% of CPS-1, which is the condensate (A), 49% of toluene, and 19% of ethanol.

(Example 3 [Production of condensate (A)])
In a flask similar to that of Example 1, 91 g of toluene, 33.6 g (0.30 mol) of citraconic anhydride and 0.063 g of MQ were charged, and while stirring at room temperature, 57.3 g of γ-aminopropylmethyldiethoxysilane (0.3. 30 mol) was added dropwise.
This was stirred at 50 ° C. for 1 hour and then refluxed for 5 hours with stirring in an oil bath at 125 ° C. to obtain a toluene-ethanol mixed solvent solution of the condensate (A).
As a result of removing a small amount of the obtained solution and removing the solvent and measuring the ¹ H-NMR spectrum of the condensate (A), R ¹ is a methyl group and R ² is a hydrogen atom in formula (1) and formula (2). , R is a propylene group, R ⁰ is a methyl group, R ³ is an ethyl group, x is 1, y is 0, z is 0.2, and a is a condensate.
Further, the obtained condensate (A) was subjected to GPC measurement in the same manner as in Example 1. As a result, Mw was 970.
Hereinafter, the condensate (A) obtained here is referred to as CS-2.
This product was a solution containing 37% of CS-2 as the condensate (A), 50% of toluene, and 13% of ethanol.

(Example 4 [Production of condensate (A)])
In a flask similar to Example 1, 97 g of toluene, 33.6 g (0.30 mol) of citraconic anhydride and 0.062 g of MQ were charged, and 44.2 g (0.20 mol) of γ-aminopropyltriethoxysilane was stirred at room temperature. ) And 19.1 g (0.10 mol) of γ-aminopropylmethyldiethoxysilane were added dropwise.
This was stirred at 50 ° C. for 1 hour, then refluxed for 4 hours with heating and stirring in a 125 ° C. oil bath, and then allowed to stand overnight at room temperature.
Next, 1.8 g (0.10 mol) of water was added, and the mixture was refluxed for 5 hours with heating and stirring in an oil bath at 115 ° C. to obtain a toluene-ethanol mixed solvent solution of the condensate (A).
As a result of removing a small amount of the obtained solution and removing the solvent and measuring the ¹ H-NMR spectrum of the condensate (A), R ¹ is a methyl group and R ² is a hydrogen atom in formula (1) and formula (2). , R is a propylene group, R ⁰ is a methyl group, R ³ is an ethyl group, x is 1, y is 0, z is 0.4, and a is 0.33.
Moreover, as a result of GPC measurement of the obtained condensate (A) by the same method as in Example 1, Mw was 1,270.
Hereinafter, the condensate (A) obtained here is referred to as CS-3.
This product was a solution containing 34% of the condensate (A) CS-3, 50% of toluene and 16% of ethanol.

(Examples 5 to 10 and Comparative Example 1)
<Production of active energy ray-curable 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.

In addition, the abbreviation of Table 1 means the following.
CS-1: Condensate obtained in Example 1 (3A)
CPS-1: Condensate (A) obtained in Example 2
CS-2: Condensate obtained in Example 3 (A)
CS-3: Condensate (A) obtained in Example 4
DPHA: polyfunctional acrylate mainly composed of dipentaerythritol hexaacrylate, Aronix M-402 manufactured by Toagosei Co., Ltd.
DETX: 2,4-diethylthioxanthone, Nippon Kayaku Co., Ltd. Kayacure DETX-S.
Irg184: 1-hydroxycyclohexyl-phenyl-ketone, Irgacure 184 manufactured by Ciba.
-PGM: Propylene glycol monomethyl ether.
In Table 1, the number of parts of CPS-1, CS-2, and CS-3 represents the number of parts by weight of the condensate (A) contained in Example 2, Example 3, and Example 4, respectively. In the actual formulation, products containing toluene and ethanol were used as they were.

<Method of hard coat treatment>
As a base material, a cycloolefin polymer (ZEONOR-1420, thickness 0.20 mm, hereinafter abbreviated as untreated Zeo or Zeo) manufactured by Nippon Zeon Co., Ltd., and a corona-treated one (hereinafter referred to as C-Zeo). And a polycarbonate plate (thickness 1.0 mm, hereinafter also abbreviated as PC) obtained from Engineering Test Service Co., Ltd. was used. As for the size of the substrate, Zeo and C-Zeo were A4 size, and PC was 7 cm × 15 cm.
On these substrates, the composition shown in Table 1 was applied with a bar coater so that the coating thickness after drying was 7 μm, dried with a hot air dryer at 100 ° C. for 3 minutes, and then immediately irradiated with ultraviolet rays. A hard coat cured film was prepared.
For UV irradiation, an electrodeless lamp (H bulb) manufactured by Fusion Ubui Systems Japan Co., Ltd. is used, the lamp height is the focal length of the condenser mirror (10 cm), and the conveyor speed is 10 m / min. Irradiated. The irradiation energy per pass was 500 mJ / cm ² in the UV-A region of UV POWER PUCK manufactured by EIT (total 3000 mJ / cm ² ).
The obtained cured film (hereinafter referred to as “test body”) was evaluated by the following method. Note that the brackets of the test specimen mean the base material used.

<Evaluation method>
(Odor after curing)
Check the odor of the test specimen (C-Zeo) immediately after UV irradiation, ○ if no odor was generated from the test specimen (C-Zeo), △ if the odor was felt a little, odor generated What was was evaluated as x.

(Smoothness)
In the test body (C-Zeo, PC), the case where the cured coating film was smooth visually was evaluated as ◯, the case where there was a slight coating unevenness was evaluated as Δ, and the case where there was repelling was evaluated as x.

(Visual transparency)
In the test body (C-Zeo, PC), a sample having no visual turbidity was evaluated as ◯, a sample having slight turbidity was evaluated as Δ, and a sample that was clearly turbid was evaluated as ×.

(Haze)
The specimen (C-Zeo) was cut into a size of 10 cm × 10 cm, and the haze was measured with a standard light D65 using a haze meter NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. The haze of C-Zeo before the hard coat treatment was 0.4%.

(warp)
The test body (C-Zeo) was cut into a size of 10 cm × 10 cm, placed on a smooth glass plate with the hard coat surface facing up, and the heights raised at the four corners were measured to calculate an average value (mm).

(Chips)
The degree of powder (chip) generated when the test specimen (C-Zeo) was cut with a cutter was visually determined and evaluated as follows.
○: No chips at all △: Some chips are generated ×: Many chips are generated

(Abrasion resistance)
While applying a 1 kg load on steel wool # 0000 of 2 cm × 2 cm, the hard coat surface of the specimen (C-Zeo, PC) was reciprocated 50 times, and the situation of the scratch was judged visually and evaluated as follows. did.
◎: No scratches ○: There are several scratches △: There are many scratches, but haze is less than 5% x: Whitening and haze is 5% or more In addition, in C-Zeo that is not hard-coated, it is whitened and haze Became 25%.

(Adhesion)
In accordance with JIS K5400, 100 grids were made by cutting 11 mm long and horizontal cuts with a cutter on the hard coat surface of the specimen (C-Zeo, Zeo, PC). (Registered trademark) was pressure-bonded and peeled off, and was evaluated as follows according to the area% of the remaining film.
○: Remaining film rate 100%
Δ: Remaining film ratio 85-99%
X: Remaining film ratio 5 to 84%
XX: Remaining film rate 0 to 4%

(UV resistance)
The specimen (PC) was continuously irradiated with ultraviolet rays for 5 minutes by an 80 W / cm high-pressure mercury lamp (with parallel light mirror, lamp height 30 cm) manufactured by Eye Graphics Co., Ltd., and then cooled to room temperature. Irradiation was continued again for 5 minutes.
In addition, the irradiation intensity at this time is a value measured by UV POWER PUCK of EIT, UV-A is 146 mW / cm ² , UV-B is 91 mW / cm ² , UV-C is 18 mW / cm ² , UV-V Was 55 mW / cm ² (the integrated light quantity in UV-A was 87,600 mJ / cm ² ).
After this ultraviolet irradiation, the state of the cured film was visually observed and evaluated as follows.
○: No cracking is observed in the coating film Δ: Slight cracking occurs in the coating film ×: Many cracking occurs in the coating film

<Evaluation results>
The evaluation results are shown in Table 2.
As shown in Table 2, the composition of Example 5 has almost the same scratch resistance as the composition of Comparative Example 1, but does not generate any warp or chips that are defects of the hard-coated film. Moreover, since it can be hardened without an initiator, there is no decomposition of the initiator and there is a feature that no odor is generated. Furthermore, it is excellent in UV resistance.
In addition to the features of Example 5, the composition of Example 6 in which DETX, which is a photosensitizer, is blended with the condensate (A) of the present invention is also excellent in adhesion to untreated Zeo.
The composition of Example 7 in which DPHA is blended with the condensate (A) of the present invention is warped despite having excellent scratch resistance that is not inferior to that of the composition containing only DPHA of Comparative Example 1. There is absolutely no generation of chips, and UV resistance is also excellent.
The composition of Example 8 is obtained by blending DETX with CPS-1 in which a phenyl group is introduced into 30 mol% of the organic group of the condensate (A), and has the same features as the composition of Example 6. Have.
The composition of Example 9 is a composition of CS-2, which is a condensate of dialkoxysilane (A), and DPHA and DETX. The composition of Example 6 is the same as that of Example 6 except that a small amount of chips are generated. It has the same features.
The composition of Example 10 is a blend of CS-3, which is a condensate (A) having a molar ratio of trialkoxysilane to dialkoxysilane of 2: 1, and DPHA and DETX. It has the same features as the above composition.
On the other hand, in the composition of Comparative Example 1, the cured film had an odor, the smoothness was insufficient, the warp occurred, and a lot of chips were generated. Further, the UV resistance was insufficient.

  * 1) Since the liquid was biased due to intense repelling, evaluation as a coating film could not be performed.

  The curable composition of the present invention can be suitably used as an active energy ray curable composition, and can be particularly suitably used as an active energy ray curable composition for hard coat.

1 represents the ¹ H-NMR spectrum of the condensate (3A) obtained in Example 1.

Claims (11)

The curable composition containing the condensate (A) of the alkoxysilane containing the structural unit represented by following General formula (1).
[(P—SiO _3/2 ) _1-a (P—Si (R ⁰ ) O _2/2 ) _a ] _x (Q—SiO _3/2 ) _y (O _1/2 R ³ ) _z. 1)
However, in the general formula (1), P represents a group represented by the following general formula (2), Q represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group or a hydrogen atom, R ³ is a hydrogen atom or R ¹ represents a monovalent organic group, R ⁰ represents an alkyl group having 1 to 6 carbon atoms, x represents a positive number, y, z and a represent 0 or a positive number, x + y = 1, 0. Satisfying the conditions of 3 ≦ x ≦ 1, 0 ≦ y ≦ 0.7, 0 ≦ z ≦ 2 and 0 ≦ a ≦ 1, and P, Q, R ⁰ and R ³ in one molecule are each two or more types Different groups may be included, and Q and R ⁰ , Q and R ³ , or R ⁰ and R ³ in one molecule may be the same group or different groups. Also good.

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 curable composition according to claim 1, wherein y is 0 in the general formula (1).   The curable composition according to claim 1 or 2, wherein R in the general formula (2) is an alkylene group. In the said General formula (2), ^one of R < ¹ > and R < ² > is a hydrogen atom, and the other is an alkyl group, The curable composition in any one of Claims 1-3.   The curable composition according to any one of claims 1 to 4, wherein the condensate (A) has a weight average molecular weight of 500 to 100,000.   An active energy ray-curable composition comprising the composition according to claim 1.   The active energy ray-curable composition according to claim 6, further comprising a compound other than the condensate (A) having a total of 2 to 10 (meth) acryloyl groups and / or maleimide groups in one molecule.   The active energy ray-curable composition according to claim 6 or 7, which is used for a hard coat.   An article formed by forming a cured film of the composition according to any one of claims 1 to 8 on a surface of a substrate. A compound containing a structural unit represented by the following general formula (3) and having a weight average molecular weight of 500 to 100,000.
(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 a monovalent organic group having 1 to 8 carbon atoms, z is 0 or a positive number And 0 ≦ z ≦ 2.

In the general formula (4), one of R ⁴ and R ⁵ represents a hydrogen atom, the other represents an alkyl group having 1 to 6 carbon atoms, and R ⁶ represents an alkylene group having 2 to ⁶ carbon atoms. Adding an aminoalkyltrialkoxysilane and / or aminoalkyl (alkyl) dialkoxysilane to the carboxylic acid anhydride having a double bond represented by the general formula (16) to form an amic acid; and
A method for producing a condensate of alkoxysilane, comprising a step of cyclizing the amic acid to form a maleimide group, and consuming water generated by the ring-closure reaction by a hydrolysis reaction of the alkoxy group.

In the general formula (16), 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.

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