JPWO2020130072A1 - Coating agent, coating film and laminate - Google Patents

Abstract

The present invention is a silane condensate having a structure (A) represented by the following formula (1), a structure (B) represented by the following formula (3), and one or both of urethane or urea bonds. The present invention provides a coating agent, which is characterized by containing. Further, the present invention provides a coating film obtained by curing the coating agent. Further, the present invention provides a laminate having the coating film. ... (1) ... (2) [Chemical 3] ... (3)

Description

The present invention provides a coating agent containing a silane condensate having a specific structure, and a coating film obtained by curing the coating agent. It also provides a laminate containing the coating film.

In recent years, the use of transparent resin materials as a substitute for glass has been increasing. In particular, polycarbonate resin and the like are widely used because they are excellent in heat resistance, impact resistance, and transparency. However, since polycarbonate resin and the like are inferior in scratch resistance, weather resistance, and the like as compared with glass, a hard coat material that protects the surface thereof has been proposed.

In general, as a means for improving wear resistance, a hard coat layer needs to have a high hardness, and many coating materials using an organosiloxane composition have been proposed. However, when the hardness is increased, the obtained film is brittle, and there is a problem that the adhesion to the resin base material is lowered and the difference in the behavior of environmental dimensional change from the resin base material is large, so that cracks are likely to occur. Therefore, a method of blending an acrylate compound or a urethane compound has been proposed for the purpose of improving brittleness and adhesiveness, but it has a drawback that wear resistance is lowered, and a hard coat for automobile windows, which is particularly required for visibility, is attached. It is insufficient to satisfy the wear resistance, adhesion and weather resistance equivalent to glass such as a resin substrate (resin glazing). In order to improve this, a primer layer with good adhesion to both layers is provided between the resin base material and the hard coat layer, and the hard coat layer has abrasion resistance and weather resistance, and the primer layer has weather resistance and adhesion. A method with separate functions has been proposed.

For example, a structure in which a silicon oxide film is deposited on the surface of a polycarbonate substrate by a thermosetting film of an acrylic resin, a thermosetting film of an organosiloxane-based resin, or a plasma-induced chemical vapor deposition method (CVD method) using an organosilicon compound as a raw material. Has been proposed. However, although this laminated body has improved weather resistance and wear resistance, it requires a dry process process such as a vacuum chamber for depositing a silicon oxide film, so that the process cost is high and the load on general-purpose popularization is large. It can be said that. Further, a method of applying and curing a thermosetting silicone resin has also been proposed. Since this method can form a film by a wet process, the process cost is low, but the high temperature and long time required for curing result in poor productivity, and the wear resistance is not sufficiently satisfactory.
In order to solve the above problems, Patent Document 3 proposes a coating agent that can form a film by a wet process and protects the surface of an organic resin substrate that can be produced in a short time by curing with ultraviolet rays. As a result of examination by the present inventor, the wear resistance, the moisture heat resistance, the cold heat resistance, and the weather resistance are not satisfied.

Tokushu Kohei No. 3-4504 Japanese Patent No. 4462421 JP-A-2018-104618

An object of the present invention is to provide a coating agent capable of producing a coating film having excellent wear resistance, weather resistance, cold heat resistance, and moisture heat resistance. Another object of the present invention is to provide a laminate having the coating film.

As a result of diligent studies, the present inventors have found that the above problems can be solved by providing a coating agent containing a silane condensate having a specific structure and a coating film obtained by curing the coating agent. I found it.

That is, the present invention
It contains a structure (A) represented by the following formula (1), a structure (B) represented by the following formula (3), and a silane condensate having either or both of urethane and urea bonds. It is intended to provide a coating agent, which is characterized by the above.

・・・（１）

... (1)

(In the formula, X _{1 to} X ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a group represented by the formula (2), _{and at least one of X 1 to} X ₃ is the formula (2). ) Is the group represented by.

・・・（２）

... (2)

(In the formula, R ¹ represents an alkyl group having 1 to 15 carbon atoms.
Y ₁ is a bonding group having one or more of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond, and n 1 represents an integer of 1 to 3. )))

・・・（３）

... (3)

(In the formula, R ² indicates an alkyl group having 1 to 15 carbon atoms, and R ³ indicates a hydrogen atom or a methyl group.
Y ₂ is a bonding group having one or more of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond, n2 represents an integer of 1-3, and n3 represents an integer of 1-3. show. (In the formula, the oxygen atom bonded to the Si atom may be shared with the oxygen atom bonded to the Si atom in the above formula (1).)

The present invention also provides a coating agent having a structure in which any one of _{Y 1} and / or Y _{2 is represented by the following formula (4).}

・・・（４）

... (4)

(In the formula, R ^{4 to} R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Z indicates a bonding group having a urea or urethane bond, n3 indicates a number of 1 to 3, l indicates a number of 1 to 10, and m indicates a number of 1 to 10).

The present invention also provides the coating agent, wherein the silane condensate contains the structure (C) represented by the following formula (5).

・・・（５）

... (5)

Further, the present invention contains a compound (A1) represented by the formula (6) and a compound (B1) represented by the formula (8), and at least one of the compound (A1) and the compound (B1) is contained. Provided are a coating agent containing a condensate of a composition characterized by having at least one of urethane or urea bonds.

・・・（６）

... (6)

_(Wherein, X 4 to X ₆ are each independently a hydrogen atom, an alkyl group or a group represented by the formula (6) of 1 to 15 carbon _atoms, at least one of the formula X 4 to X ₆ (7 ) Is the group represented by.

・・・・（７）

・ ・ ・ ・ (7)

Y ₃ is a bonding group having one or more of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond, and in the formula, R ¹⁰ represents an organic group having 1 to 15 carbon atoms, and R ^{Reference numeral 11} indicates an alkyl group or a hydrogen atom having 1 to 15 carbon atoms. n4 represents an integer of 1 to 3.

・・・（８）

... (8)

(In the formula, R ¹² and R ¹³ indicate an alkyl group or a hydrogen atom having 1 to 15 carbon atoms, and R ¹⁴ indicates a hydrogen atom or a methyl group.
Y ₄ represents an alkyl group having 1 to 10 carbon atoms, a linking group having any one or more of the urea bond and urethane bond, n5 is an integer of 1 to 3, a is an integer of from 1 to 3 n6 show. )

Further, the present invention is _{a coating agent, characterized in that any one of Y 3} and / or Y ₄ has a structure represented by the following formula (8).

・・・（９）

... (9)

(In the formula, R ^{15 to} R ¹⁸ independently indicate a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹⁹ independently indicate a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, respectively, and Z Indicates a bonding group having a urea or urethane bond, n7 indicates a number of 1 to 3, l indicates a number of 1 to 10, and m indicates a number of 1 to 10.)

The present invention also provides a coating film obtained by curing the coating agent.

The present invention also provides a laminate containing the coating film.

The coating film of the present invention can obtain a coating film having excellent wear resistance, weather resistance and cold heat resistance, particularly long-term weather resistance. Furthermore, since it is excellent in moisture resistance and moldability, it can be suitably used for hard coats, especially for outdoor applications.

The present invention is a silane condensate having a structure (A) represented by the following formula (1), a structure (B) represented by the following formula (3), and one or both of urethane or urea bonds. A coating agent, characterized by containing.

・・・（１）

... (1)

(In the formula, R ¹ represents an alkyl group having 1 to 15 carbon atoms, and X _{1 to} X ₃ each independently represent a hydrogen atom, an alkyl having 1 to 15 carbon atoms or a group represented by the formula (2). , X _{1 to} X ₃ are groups represented by the formula (2).

・・・（２）

... (2)

(In the formula, R ¹ represents an alkyl group having 1 to 15 carbon atoms, and Y ₁ is a bonding group having one or more of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond. n1 indicates an integer of 1 to 3)))

・・・（３）

... (3)

(In the formula, R ² indicates an alkyl group having 1 to 15 carbon atoms, R ³ indicates a hydrogen atom or a methyl group, and Y ₂ indicates an alkyl group having 1 to 10 carbon atoms, any one of a urea bond and a urethane bond. In the bonding group having one or more, n2 represents an integer of 1 to 3 and n3 represents an integer of 1 to 3 (in the formula, the oxygen atom bonded to the Si atom is the above formula (1). ), It may be shared with the oxygen atom bonded to the Si atom.)

The coating agent of the present invention is a condensate having an isocyanul ring structure and a (meth) acryloyl group, and is characterized by having a urea bond or a urethane bond in the condensate. Having a urea bond or a urethane bond in the condensate improves the moist heat resistance of the obtained coating film. Further, the moldability and cold heat resistance are improved by the action of the urea bond or the urethane bond. The urea bond and the urethane bond may have one or more of either one type in the condensate, or may have one or more of the two types, respectively.

The urea bond and urethane bond may be introduced anywhere in the condensate, but are preferably present in Y ₁ in the formula (2) and / or in Y ₂ in the formula (3). Is preferable.

In the condensate, the preferred structure is _{a coating agent, characterized in that any one of Y 1} and / or Y ₂ has a structure represented by the following formula (4).

・・・（４）
（式中、Ｒ^４〜Ｒ^９はそれぞれ独立して水素原子又は炭素数１〜５のアルキル基を示し、
Ｚはウレアまたはウレタン結合を有する結合基を示し、ｎ３は１〜３の数を示し、ｌは１〜１０の数を示し、ｍは１〜１０の数を示す

... (4)
(In the formula, R ^{4 to} R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Z indicates a bonding group having a urea or urethane bond, n3 indicates a number of 1 to 3, l indicates a number of 1 to 10, and m indicates a number of 1 to 10.

The R ^{4 to} R ⁹ are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, but are preferably hydrogen atoms or alkyl groups having 1 to 2 carbon atoms, and more preferably hydrogen atoms. .. Further, the number of n3 is 1 to 3, but it is preferably 1. Further, l is a number of 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The m is a number of 1 to 10, preferably 1 to 8, and more preferably 1 to 6.

<Structure (A)>
The structure A of the present invention is a structure having an isocyanul ring represented by the above formula (1). In the structure (A), X _{1 to} X ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a group represented by the formula (2), and at least one of them is represented by the formula (2). Is the basis for being done.
In the formula (1), _preferably, a group represented by at least 2 Exemplary ethynylphenylbiadamantane derivatives of X 1 to X ₃ (2), more preferably both are three _X 1 to X ₃ is expressed by equation (2) It is preferable that n1 is selected from 2 or 3.

<Structure B>
The structure B of the present invention is a structure having a (meth) acryloyl group represented by the above formula (3). In the formula (3), Y ₂ is preferably a urethane bond or a bonding group in which a urea bond and an alkyl group are combined, n2 is preferably selected from 2 to 3, and n3 is selected from 1 to 2. Is preferable.

The silane condensate of the present invention is a condensate having the above-mentioned structure (A) and structure (B), but if it further has a structure represented by the following formula (5), it has a hard coat property. It is preferable because it improves.

・・・（５）

... (5)

<Composition>
The method for producing the silane condensate of the present invention is not particularly limited, but contains the compound (A1) represented by the formula (6) and the compound (B1) represented by the formula (8), and the compound ( It can be suitably produced by condensing a composition characterized in that at least one of A1) and the compound (B1) has a urethane or urea bond.

・・・（６）

... (6)

_(Wherein, X 4 to X ₆ are each independently a hydrogen atom, a group represented by the alkyl group or the formula 1 to 15 carbon atoms _(7), at least Exemplary ethynylphenylbiadamantane derivatives (7 X 4 to X ₆ ) Is the group represented by.

・・・・（７）

・ ・ ・ ・ (7)

(In the formula, Y ₃ is a bonding group having one or more of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond, and in the formula, R ¹⁰ is an alkyl group having 1 to 15 carbon atoms. , And R ¹¹ represents an alkyl group or a hydrogen atom having 1 to 15 carbon atoms.

・・・（８）

... (8)

(In the formula, R ¹² and R ¹³ indicate an alkyl group or a hydrogen atom having 1 to 15 carbon atoms, R ¹⁴ indicates a hydrogen atom or a methyl group, and Y ₄ indicates an alkyl group having 1 to 10 carbon atoms, a urea bond and a urea bond. A bonding group having any one or more of the urethane bonds, where n5 represents an integer of 1 to 3 and n6 represents an integer of 1 to 3.

A preferred structure is a _{coating agent, characterized in that any one of Y 3} and / or Y ₄ has a structure represented by the following formula (9).

・・・（９）

... (9)

(In the formula, R ^{15 to} R ¹⁸ independently indicate a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹⁹ independently indicate a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, respectively, and Z Indicates a bonding group having a urea or urethane bond, n7 indicates a number of 1 to 3, l indicates a number of 1 to 10, and m indicates a number of 1 to 10.)

<Compound (A1)>
In the compounds of the formula (6) _(A1), a group represented by at least 1 Exemplary ethynylphenylbiadamantane derivatives of X 4 ~X ₆ (7). _Preferably, a group represented by at least 2 Exemplary ethynylphenylbiadamantane derivatives of X 4 to X ₆ (7), more preferably when both are three _X 4 to X ₆ is a group represented by the formula (7) .. Further, n4 is preferably selected from 2 or 3.

The compound (A1) represented by the formula (6) can be roughly classified into a compound having a urea bond or a urethane bond and a compound having no urea bond or a urethane bond.
Specific examples of the compound having a structure having no urea bond or urethane bond include 1,3,5-tris (methyldimethoxysilylpropyl) isocyanurate and 1,3,5-tris (methyldiethoxysilylpropyl). Isocyanurate, 1,3,5-tris (trimethoxysilylpropyl) isocyanurate, 1,3,5-tris (trimethoxysilylethyl) isocyanurate, 1,3- (di-2-propen-1-yl) -5- (3-Triethoxysilylpropyl) isocyanurate, 1- (2-propen-1-yl) -3,5-bis (3-triethoxysilylpropyl) isocyanurate, 1,3-bis (3-bis) Trimethoxysilylpropyl) isocyanurate, 1-glycidylmethyl-3,5-bis (3-trimethoxysilylpropyl) isocyanurate, 1,3-bis (glycidylmethyl) -5- (3-trimethoxysilylpropyl) isocia Nurate, 1-glycidylmethyl-3- (2-propen-1-yl) -5- (3-triethoxysilylpropyl) isocyanurate, 1,3-dimethyl-5- (3-triethoxysilylpropyl) isocyanurate And so on. Preferred examples thereof include 1,3,5-tris (trimethoxysilylpropyl) isocyanurate and 1,3,5-tris (triethoxysilylpropyl) isocyanurate.

Further, as the compound (A1) represented by the formula (6), in the case of a compound having a urea bond structure, it can also be obtained by reacting an isocyanurate compound having an isocyanate group with an alkoxysilane compound having an amino group. can.

Examples of the isocyanurate compound having an isocyanate group include an isocyanurate form of 1,6 hexanediisocyanate, an isocyanurate form of 1,5-pentanediisocyanate, an isocyanurate form of isophorone diisocyanate, an isocyanurate form of dicyclohexylmethane 4,4-diisocyanate, 1, Examples thereof include isocyanurates of 3-bisisocyanatemethylcyclohexane and isocyanurates of 1,4-bisisocyanatemethylcyclohexane. It is preferably an isocyanurate form of 1,5 pentane diisocyanate or an isocyanurate form of 1,6 hexanediisocyanate.

Examples of the alkoxysilane compound having an amino group include 3-aminopropyltrialkoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, 8-aminooctyllyalkoxysilane, and 3-aminopropylmethyldialkoxysilane. , N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, 8-aminooctylmethyldialkoxysilane and the like. Preferred is 3-aminopropyltrialkoxysilane.

<Compound (B1)>
In the compound (B1) represented by the formula (8),
In the formula, R ¹⁴ is preferably a hydrogen group, n5 is preferably an integer of 2 to 3, more preferably 3, and n6 is preferably an integer of 1 to 2, more preferably 1.

It is preferable that any one of Y ₃ and / or Y ₄ has a structure represented by the following formula (9). Wherein ^{(9), R} 15 ~R ¹⁹ is preferably a methyl group or hydrogen group, more preferably a hydrogen group. Further, the number of n7 is 1 to 3, but it is preferably 1.
Further, l is a number of 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The m is a number of 1 to 10, preferably 1 to 9, and more preferably 1 to 8.

The compound (B1) represented by the formula (8) can be roughly classified into a compound having a urea bond or a urethane bond and a compound having no urea bond or a urethane bond.
Compounds having a structure that does not have a urea bond or a urethane bond include 3-propyl (meth) acryloyltrimethoxysilane, 3-propyl (meth) acryloyltriethoxysilane, 8-octyl (meth) acryloyltrimethoxysilane, and 8-propyl (meth) acryloyltrimethoxysilane. Octyl (meth) acryloyltriethoxysilane, 10-decane (meth) acryloyltrimethoxysilane, 10-decane (meth) acryloyltriethoxysilane, 3-propyl (meth) acryloylmethyldimethoxysilane, 3-propyl (meth) acryloylmethyl Diethoxysilane, 8-octyl (meth) acryloylmethyldimethoxysilane, 8-octyl (meth) acryloylmethyldiethoxysilane, 10-decane (meth) acryloylmethyldimethoxysilane, 10-decane (meth) acryloylmethyldiethoxysilane, etc. Can be mentioned.

Among the compounds (B1) represented by the formula (8), the compound having a urethane bond structure can be obtained by reacting a silane compound having an isocyanate group with a (meth) acrylate compound having a hydroxyl group. can.

Examples of the silane compound having an isocyanate group include 3-isocyanatepropyltriethoxysilane, 5-isocyanatepentyltriethoxysilane, 6-isocyanatehexyltriethoxysilane, and 8-isocyanateoctyltriethoxysilane. Of these, 3-isocyanatepropyltriethoxysilane is preferable.

Examples of the (meth) acrylate compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-. Hydroxy-1-methylethyl (meth) acrylate, 2-hydroxy-butyl (meth) acrylate, 1-ethyl-2-hydroxy-ethyl (meth) acrylate, 2-hydroxy-pentyl (meth) acrylate, 2-hydroxy-1 -Propylethyl (meth) acrylate, 3-hydroxy-butyl (meth) acrylate, 3-hydroxy-2-methylpropyl (meth) acrylate, 3-hydroxy-pentyl (meth) acrylate, 2-ethyl-3-hydroxy-propyl (Meta) acrylate, 1-ethyl-3-hydroxy-propyl (meth) acrylate, 3-hydroxy-hexyl (meth) acrylate, 3-hydroxy-2-propylpropyl (meth) acrylate, 3-hydroxy-1-propylpropyl (Meta) acrylate, 4-hydroxy-pentyl (meth) acrylate, 4-hydroxy-3-methylbutyl (meth) acrylate, 4-hydroxy-2-methylbutyl (meth) acrylate, 4-hydroxy-1-methylbutyl (meth) acrylate , 4-Hydroxy-hexyl (meth) acrylate, 3-ethyl-4-hydroxy-butyl (meth) acrylate, 2-ethyl-4-hydroxy-butyl (meth) acrylate, 1-ethyl-4-hydroxy-butyl (meth) ) Acrylate, 4-hydroxy-heptyl (meth) acrylate, 4-hydroxy-3-propylbutyl (meth) acrylate, 4-hydroxy-2-propylbutyl (meth) acrylate, 4-hydroxy-1-propylbutyl (meth) Examples thereof include acrylates, glycerinji (meth) acrylates, pentaerythritol tri (meth) acrylates, and reactants with amino-based (meth) acrylates. In addition, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, trade name "Plaxel" manufactured by Daicel Chemical Industry Co., Ltd.), phthalic acid and propylene. Examples thereof include mono (meth) acrylate of polyester diol obtained from glycol. Of these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable.

Among the compounds (B1) represented by the formula (8), the compound having a structure having a urea bond is obtained by reacting a silane compound having an amino group with a (meth) acrylate compound having an isocyanate group. Can be done. Alternatively, it can be obtained by reacting a silane compound having an isocyanate group with a (meth) acrylate compound having an amino group.

Examples of the silane compound having an amino group include amino groups such as 3-aminopropyltriethoxysilane, 8-aminooctyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, and 8-aminooctylmethyldiethoxysilane. It is an alkoxysilane or the like. Of these, 3-aminopropyltriethoxylan is preferable.

Examples of the (meth) acrylate compound having an isocyanate group include 2-isocyanate ethyl (meth) acrylate, 3-isocyanatepropyl (meth) acrylate, 2-isocyanatepropyl (meth) acrylate, 4-isocyanatebutyl (meth) acrylate, and 6. -Isocyanate hexyl (meth) acrylate, 8-isocyanate octyl (meth) acrylate, 10-isocyanate decane (meth) acrylate and the like. Of these, 2-isocyanate ethyl (meth) acrylate, 3-isocyanatepropyl (meth) acrylate, 2-isocyanatepropyl (meth) acrylate, and 4-isocyanatebutyl (meth) acrylate are preferable.

As the silane compound having an isocyanate group, a silane compound used for producing a compound having a urethane bond structure among the compound (B1) can be used. Preferred is 3-isocyanatepropyltriethoxysilane.

Examples of the (meth) acrylate compound having an amino group include 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 4-aminobutyl (meth) acrylate, and 6-. Examples thereof include aminohexyl (meth) acrylate and 8-aminooctyl (meth) acrylate. Preferred are 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 4-aminobutyl (meth) acrylate.

The compounding ratio of the compound (A1) and the compound (B1) is not particularly limited, but the molar ratio is preferably 1: 4 to 1:50. This range is excellent from the viewpoint of moisture resistance and heat resistance. More preferably, it is 1: 6 to 1:20.

Compound (A1) and the compound in (B1), it is preferred that at least one of wherein Y ₃ or Y ₄ is a linking group having a urea bond or urethane bond. This is because when this portion has a urea bond or a urethane bond, the obtained condensate is excellent in moisture resistance and moldability. Preferably, _{any one of Y 3} and / or Y ₄ has a structure represented by the following formula (9).

・・・（９）

... (9)

(In the formula, R ^{15 to} R ¹⁹ each independently indicate a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Z indicates a bonding group having a urea or urethane bond, and n7 indicates a number of 1 to 3. , L indicates a number from 1 to 10, and m indicates a number from 1 to 10.)

The R ^{15 to} R ¹⁸ are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, but are preferably hydrogen atoms or alkyl groups having 1 to 2 carbon atoms, and more preferably hydrogen atoms. .. Further, the number of n7 is 1 to 3, but it is preferably 1. Further, l is a number of 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The m is a number of 1 to 10, preferably 1 to 8, and more preferably 1 to 6.

Further, the silane condensate of the present invention preferably has a structure (C) represented by the formula (5).
The structure (C) can also be introduced by condensing the compound (A1) and the compound (B1), but it is preferable to add alkoxysilane and copolymerize.

The alkoxysilane is not particularly limited, but is preferably dialkoxysilane, trialkoxysilane, or tetraalkoxysilane. Of these, trialkoxysilane and / or tetraalkoxysilane are preferred.

Specific examples of the dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, 3-glycidylpropylmethyldiethoxysilane, and 2- (3,4). -Epoxycyclohexyl) ethylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, N-2- (aminoethyl) ) 3-Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldiethoxysilane, methylcyclohexyldimethoxysilane, methylphenyldimethoxysilane and the like can be mentioned.

Specific examples of the trialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, iso-butyltrimethoxysilane, and cyclohexyltrimethoxy. Silane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-glycidylpropyltrimethoxylane, 3-glycidylpropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3 Examples thereof include −aminopropyltriethoxysilane, 3-ureidopropyltriethoxylane, and N-phenyl-3-aminopropyltrimethoxysilane.

Specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropixisilane, tetrabutoxysilane, methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, isobutyl silicate, n-butyl silicate, and the like. Examples thereof include alkyl silicates such as n-pentyl silicate and acetyl silicate.

<Mixing ratio>
The composition of the present invention contains the compound (A1) and the compound (B1).
The compounding ratio of the compound (A1) and the compound (B1) is preferably 1: 4 to 1:50 as a molar ratio. More preferably, it is 1: 6 to 1:20.

When the composition of the present invention further contains alkoxysilane, the blending amount is preferably 200 mol% or less with respect to the total molar amounts of (A1) and (B1). More preferably, it is 150 mol% or less.

The composition of the present invention may contain other formulations.
Other formulations include various resins, reactive compounds, catalysts, polymerization initiators, organic fillers, inorganic fillers, organic solvents, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, etc. Used for flow modifiers, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers, and other silane condensates having the above structure, as well as other silane condensates, such as condensation. It is a single or composite condensate of each silane compound.

<Condensation method>
The condensate of the present invention is a silane condensate having either a structure (A) represented by the formula (1), a structure (B) represented by the following formula (3), or a urethane or urea bond. Is. As a preferable method for producing the condensate of the present invention, a composition containing the compound (A1) represented by the formula (6) and the compound (B1) represented by the formula (7) is hydrolyzed and condensed. Is to let.

As a method of hydrolysis, it is preferable to hydrolyze the solution with acidic water having a pH of 1 to 7. For this pH adjustment, hydrochloric acid, nitrate, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, methanesulfonic acid, toluenesulfonic acid, phosphoric acid, etc. Organic acids and inorganic acids can be used. Further, a solid acid catalyst such as a cation exchange resin having a carboxylic acid group or a sulfonic acid group on the surface may be used as the catalyst. The amount of the acid or acid catalyst used is 0.0001 to 20% by weight based on the product.

The presence of water is required for the hydrolysis reaction. The amount of water may be an amount sufficient to hydrolyze (a part of) the hydrolyzable groups in the silane compound or the silicate compound, and may be 0, which is the theoretical amount (mol) of the number of hydrolyzable groups. The amount is preferably 5 to 5.0 times the molar amount. If the acidic catalyst is added as an aqueous solution, the water is added to the calculation. When the amount of water is small, sufficient hydrolysis does not proceed, and when the amount of water is large, the remaining water reduces the coatability and drying efficiency.

A dehydration condensation reaction of silanol groups generated at the same time as hydrolysis occurs to form a siloxane resin. The temperature at which this condensation is carried out is normal temperature or heating at 120 ° C. or lower, and more preferably 30 ° C. or higher and 100 ° C. or lower. When the temperature is low, the hydrolysis and condensation reactions take a long time and the productivity is low, and when the temperature is higher than the range, insolubilization may occur.

It is preferable to mix an organic solvent for the purpose of adjusting the reaction rate of the hydrolysis and condensation and the molecular weight of the resin to be produced. For example, alcohols include methanol, ethanol, butanol, isobutanol, isopropyl alcohol, propanol, t-butanol, sec-butanol, benzyl alcohol, and ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc. Diacetone alcohol, as ester type, ethyl acetate, methyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, butyl lactate, ethers, Isopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycol ester type as ethylene glycol monoethyl ether acetate, methoxypropyl acetate, butyl carbitol acetate, Ethylcarbitol acetate and glycol ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl diglycol, methyl triglycol, 1-methoxy-2-propanol, propylene glycol monobutyl ether and 3-methoxy-3-methyl-1. -Butanol, diethylene glycol monohexyl ether, propylene glycol monomethyl ether propionate, dipropylene glycol methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and hydrogen carbonates include benzene, toluene, and xylene. Can be mentioned. These organic solvents can be used alone or in combination of two or more.

The mixing amount of the solvent is 10 parts by weight or more when the total amount of the hydrolyzed components is 100 parts by weight.
It is preferably 1000 parts by weight.

<Coating agent>
The coating agent of the present invention has a structure (A) represented by the above formula (1), a structure (B) represented by the following formula (3), and a silane condensation having either urethane or urea bond. It contains a substance.
In addition to the silane condensate having the above structure, the coating agent of the present invention may also contain other silane condensates, for example, single or composite condensates of each silane compound used for condensation.
<Other formulations>

Further, the coating agent of the present invention may contain other formulations of the silane condensate. For example, various resins, reactive compounds, catalysts, polymerization initiators, organic fillers, inorganic fillers, organic solvents, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow modifiers, cups. Ring agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers and the like may be blended.

Examples of the reactive compound include monofunctional (meth) acrylate and polyfunctional (meth) acrylate.

Examples of the monofunctional (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone-modified hydroxy (meth) acrylate (for example, trade name of Daicel Chemical Industry Co., Ltd. Praxel "), mono (meth) acrylate of polyesterdiol obtained from phthalic acid and propylene glycol, mono (meth) acrylate of polyesterdiol obtained from succinic acid and propylene glycol, polyethylene glycol mono (meth) acrylate, polypropylene glycol Examples thereof include mono (meth) acrylates, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylates, and (meth) acrylic acid adducts of various epoxy esters.

Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonandiol di (meth) acrylate, and neopentyl glycol di (). Meta) acrylate, glycerol tri (meth) acrylate modified with ethylene oxide, glycerol tri (meth) acrylate modified with propylene oxide, trimethylol propanetri (meth) acrylate, hydroxypivalic acid modified trimethylol propanetri (meth) acrylate , Trimethylol propanetri (meth) acrylate modified with ethylene oxide, Trimethylol propanetri (meth) acrylate modified with propylene oxide, Tri (meth) acrylate modified with ethylene oxide, Pentaerythritol ethoxytetra (meth) Acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (Meta) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, dipentaerythritol hexa modified with ethylene oxide. (Meta) acrylate, dipentaerythritol hexa (meth) acrylate modified with propylene oxide, urethane (meth) acrylate compound obtained by reacting isocyanate compound with alcohol compound, polyhydric alcohol with (meth) acrylic acid and polyfunctionality. Examples thereof include a polyester (meth) acrylate compound synthesized by a condensation reaction with a carboxylic acid, a bisphenol type epoxy resin or an epoxy (meth) acrylate compound synthesized by an addition reaction between a novolak type epoxy resin and (meth) acrylic acid. ..

Examples of the organic solvent include an ester solvent, a ketone solvent, an ether solvent, an aliphatic solvent, an aromatic solvent, and an alcohol solvent.
Specifically, the ester solvent is ethyl acetate-, propyl acetate, butyl acetate, the ketone solvent is acetone, 2-butanone, methyl ethyl-ketone, methyl isobutyl ketone and the like, and the ether solvent is tetrahydrofuran. Examples of the aliphatic solvent such as dioxolane include hexane and cyclohexane, examples of the aromatic solvent include toluene and xylene, and examples of the alcohol solvent include ethanol, methanol, propanol, butanol and propylene glycol monomethyl ether. ..

Further, a liquid organic polymer may be used for adjusting the viscosity. The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and is, for example, a carboxyl group-containing polymer modified product (Floren G-900, NC-500: Kyoeisha), an acrylic polymer (Floren WK-20: Kyoeisha), and the like. Examples thereof include an amine salt of a special modified phosphoric acid ester (HIPLAAD ED-251: Kusumoto Kasei), a modified acrylic block copolymer (DISPERBYK2000; Big Chemie) and the like.

As various resins, thermosetting resins and thermoplastic resins can be used.

The thermosetting resin is a resin having a property of being substantially insoluble and insoluble when cured by means such as heating or radiation or a catalyst. As a specific example, the thermosetting resin is a resin having a property of being substantially insoluble and insoluble when cured by means such as heating or radiation or a catalyst. Specific examples thereof include phenol resin, urea resin, melamine resin, benzoguanamine resin, alkyd resin, unsaturated polyester resin, vinyl ester resin, diallyl terephthalate resin, epoxy resin, silicone resin, urethane resin, furan resin, ketone resin, and xylene. Examples thereof include resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, styrene / maleic anhydride (SMA) resins, and the like. These thermosetting resins can be used alone or in combination of two or more.

The thermoplastic resin is a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethylmethacrylate resin, acrylic resin, and polyvinyl chloride resin. Polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate Resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyether sulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyether ether ketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, Shinji Examples thereof include tactical polystyrene resin and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

The resin composition of the present invention can contain a filler. For example, silica can be blended for the purpose of improving the hard coat property. The silica is not limited, and known silica fine particles such as powdered silica and colloidal silica can be used. Examples of commercially available powdered silica fine particles include Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Syldex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., and E220A manufactured by Nippon Silysia Chemical Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Chemical Ltd., SG flakes manufactured by Nippon Ita Glass Co., Ltd. and the like.
Examples of commercially available colloidal silica include metalnol silica sol manufactured by Nissan Chemical Industry Co., Ltd., IPA-ST, MEK-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, and the like. Examples thereof include ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like.

As the silica, reactive silica may be used. Examples of the reactive silica include reactive compound-modified silica. Examples of the reactive compound include a reactive silane coupling agent having a hydrophobic group, a compound having a (meth) acryloyl group, a compound having a maleimide group, and a compound having a glycidyl group.
Commercially available powdered silica modified with a compound having a (meth) acryloyl group includes Aerosil RM50, R711 manufactured by Nippon Aerosil Co., Ltd., and commercially available colloidal silica modified with a compound having a (meth) acryloyl group. Examples thereof include MIBK-SD, MIBK-SD-L, MIBK-AC-2140Z, and MEK-AC-2140Z manufactured by Nissan Chemical Industries, Ltd. Further, silica obtained by modifying with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane and then adding an acrylic acid, or a compound having 3-isocyanatepropyltriethoxysilane, a hydroxyl group and a (meth) acryloyl group is urethane. Silane modified with a chemical reaction can also be mentioned as reactive silica.

The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or indefinite shapes can be used. For example, as commercially available hollow silica fine particles, Nittetsu Mining Co., Ltd.'s Sirinax or the like can be used.
The primary particle size is preferably in the range of 5 to 200 nm. When it is 5 nm or more, the dispersion of the inorganic fine particles in the composition becomes sufficient, and when it is 200 nm or less, sufficient strength of the cured product can be maintained.

The amount of silica to be blended is preferably 3 to 60 parts by weight when the solid content of the total amount of the compound having (meth) acrylate and silica in the resin composition is 100 parts by weight.

The resin composition of the present invention may have a filler other than silica. Examples of fillers other than silica include inorganic fillers and organic fillers. The shape of the filler is not limited, and examples thereof include particle-like, plate-like, and fibrous fillers.

For example, those having excellent heat resistance include alumina, magnesia, titania, zirconia, etc .; those having excellent heat conduction include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.; Highly conductive materials include metal fillers and / or metal-coated fillers using single metals or alloys (eg, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); barriers. Examples of excellent properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, and smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, and barium sulfate. , Zinc oxide, magnesium hydroxide; barium titanate, zirconia oxide, titanium oxide, etc. as those with high refractive index; titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus as those showing photocatalytic properties. , Carbon, sulfur, terium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead and other photocatalyst metals, composites of the metals, oxides thereof, etc .; Metals such as alumina, zirconia, and magnesium oxide, and their composites and oxides; metals such as silver and copper, tin oxide, indium oxide, etc., which have excellent conductivity; Titanium oxide, zinc oxide, etc.
These inorganic fine particles may be selected in a timely manner depending on the intended use, and may be used alone or in combination of two or more. Further, since the inorganic fine particles have various properties other than the properties mentioned in the examples, they may be selected according to the timely application.

Examples of the inorganic fiber include carbon fiber, glass fiber, boron fiber, alumina fiber, silicon carbide fiber and other inorganic fibers, as well as carbon fiber, activated carbon fiber, graphite fiber, glass fiber, tungsten carbide fiber and silicon carbide fiber (silicon carbide fiber). ), Ceramic fiber, alumina fiber, natural fiber, mineral fiber such as genbuiwa, boron fiber, boron nitride fiber, boron carbide fiber, metal fiber and the like. Examples of the metal fiber include aluminum fiber, copper fiber, brass fiber, stainless fiber, and steel fiber.

Examples of the organic fiber include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate, cellulose, pulp, and the like. Examples thereof include natural fibers such as cotton, wool and silk, and regenerated fibers such as proteins, polypeptides and arginic acid.

The amount of the filler to be blended is preferably 3 to 60 parts by weight when the solid content of the total amount of the compound having (meth) acrylate and the filler in the resin composition is 100 parts by weight.

Since the composition of the present invention is cured by active energy rays, it is preferable to use a polymerization initiator, particularly a photopolymerization initiator. As the photopolymerization initiator, a known one may be used, and for example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used. Examples of the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 4 -(2-Hydroxy-ethoxy) phenyl- (2-hydroxy-2-propyl) ketone and the like can be mentioned. Examples of the benzyl ketals include 1-hydroxy-cyclohexyl-phenylketone, benzyl dimethyl ketal and the like. Examples of the benzophenones include benzophenone, methyl o-benzoylbenzoate and the like. Examples of the benzoins include benzoin, benzoin methyl ether, benzoin isopropyl ether and the like. The photopolymerization initiator may be used alone or in combination of two or more. The amount of the photopolymerization initiator used is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, based on 100% by weight of the resin solid content of the resin composition.

A light stabilizer and an ultraviolet absorber can also be introduced into the composition of the present invention. Examples of the light stabilizer include HALS having a hindered amine skeleton. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, cyclic iminoester-based, cyanoacrylate-based, and polymer-type ultraviolet absorbers.

<Surface modifier>
Various surface modifiers may be added to the composition of the present invention for the purpose of enhancing the leveling property at the time of coating, increasing the slipperiness of the cured film and enhancing the scratch resistance, and the like. As the surface modifier, various additives for modifying the surface physical characteristics, which are commercially available under the names of a surface conditioner, a leveling agent, a slipperiness-imparting agent, an antifouling property-imparting agent, and the like, can be used. Of these, silicone-based surface modifiers and fluorine-based surface modifiers are suitable. Specific examples include silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, and fluoropolymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain. Examples thereof include fluoropolymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. One or more of these may be used. A molecule containing a (meth) acryloyl group may be used for the purpose of enhancing the sustainability of slipperiness. Specific surface modifiers include EBECRYL350 (Daisel Ornex Co., Ltd.), BYK-333 (Big Chemie Japan Co., Ltd.), BYK-377 (Big Chemie Japan Co., Ltd.), BYK-378 (Big Chemie Japan Co., Ltd.). ), BYK-UV3500 (Big Chemie Japan Co., Ltd.), BYK-UV3505 (Big Chemie Japan Co., Ltd.), BYK-UV3576 (Big Chemie Japan Co., Ltd.), Mega Fuck RS-75 (DIC Co., Ltd.), Mega Fuck RS- 76-E (DIC Co., Ltd.), Megafuck RS-72-K (DIC Co., Ltd.), Megafuck RS-76-NS (DIC Co., Ltd.), Megafuck RS-90 (DIC Co., Ltd.), Megafuck RS- 91 (DIC Co., Ltd.), Megafuck RS-55 (DIC Co., Ltd.), Optool DAC-HP (Daikin Industry Co., Ltd.), ZX-058-A (T & K TOKA Co., Ltd.), ZX-201 (T & K TOKA Co., Ltd.) , ZX-202 (T & K TOKA Co., Ltd.), ZX-212 (T & K TOKA Co., Ltd.), ZX-214-A (T & K TOKA Co., Ltd.), X-22-164AS (Shinetsu Chemical Industry Co., Ltd.), X-22- 164A (Shinetsu Chemical Industry Co., Ltd.), X-22-164B (Shinetsu Chemical Industry Co., Ltd.), X-22-164C (Shinetsu Chemical Industry Co., Ltd.), X-22-164E (Shinetsu Chemical Industry Co., Ltd.), X- 22-174DX (Shinetsu Chemical Industry Co., Ltd.), etc. can be mentioned.

In the coating agent of the present invention, the blending amount of the silane condensate of the present invention is preferably 10 to 100 wt% with respect to the total amount of the non-volatile content of the coating agent. More preferably, it is 50 to 100 wt%.

<Coating film and laminate>
A coating film can be obtained by curing the coating agent of the present invention. Specifically, by applying the coating agent of the present invention to a substrate and curing it, a laminate having a coating film can be obtained.

The base material in the laminate is not particularly limited, and for example, polyolefins such as polyethylene, polypropylene and ethylene-propylene copolymer; polyesters such as polyethylene isophthalate, polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate; nylon 1 , Nylon 11, Nylon 6, Nylon 66, Nylon MX-D and other polyamides; polystyrene, styrene-butadiene block copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer (ABS resin) and the like. Stylized polymer; Acrylic polymers such as polymethylmethacrylate, methylmethacrylate / ethylacrylate copolymer, polycarbonate and the like can be used. The plastic base material may have a single layer or a laminated structure of two or more layers. Further, these plastic substrates may be unstretched, uniaxially stretched, or biaxially stretched.

Further, on the plastic substrate, a known antistatic agent, anti-fog agent, anti-blocking agent, ultraviolet absorber, antioxidant, light stabilizer, as necessary, can be used as long as the effect of the present invention is not impaired. Known additives such as crystal nucleating agents and lubricants may be contained.

The plastic substrate may be subjected to a known surface treatment on the surface of the substrate in order to further improve the adhesion to the resin composition of the present invention, and such surface treatment includes, for example, a corona discharge treatment. , Plasma treatment, frame plasma treatment, electron beam irradiation treatment, ultraviolet irradiation treatment and the like, and one or a combination of two or more of these may be performed.

The shape of the base material is not particularly limited, and may be, for example, a sheet-like, plate-like, spherical, film-like or large-sized structure, or an assembly or molded product having a complicated shape. Further, the surface of the base material may be previously coated with an undercoat paint or the like, and even if the coated portion is deteriorated, the resin composition of the present invention can be applied.

As the undercoat paint, known water-soluble or water-dispersible paints, organic solvent-type or organic solvent-dispersed paints, powder paints and the like can be used. Specifically, acrylic resin-based paint, polyester resin-based paint, alkyd resin-based paint, epoxy resin-based paint, fatty acid-modified epoxy resin-based paint, silicon resin-based paint, polyurethane resin-based paint, fluoroolefin-based paint, or amine-modified epoki. Various types such as resin paints can be used. Further, the undercoat paint may be a clear paint containing no pigment, an enamel-based paint containing the pigment, or a metallic paint containing aluminum flakes and the like.

Examples of the method for applying the resin composition or paint of the present invention to the substrate include a brush coating method, a roller coating method, a spray coating method, a dip coating method, a flow coater coating method, a roll coater coating method, or electrodeposition. It is possible to apply a known and customary painting method such as a painting method.

As a method for curing the coating liquid, since the resin composition of the present invention contains a compound having a polymerizable unsaturated group, it can be cured by irradiation with active energy rays.

The activation energy ray curing means to cure by irradiating the coated object with the active energy ray. Examples of the active energy ray include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among these, ultraviolet rays (UV) are particularly preferable from the viewpoint of curability and convenience. As the light used for curing with ultraviolet rays, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an argon laser, a helium / cadmium laser, or the like can be used. By using these to irradiate the coated surface of the coated object with ultraviolet rays having a wavelength of about 180 to 400 nm, it is possible to cure the coating film to form a cured product layer and obtain a laminated body. The irradiation amount of ultraviolet rays is appropriately selected depending on the type and amount of the photopolymerization initiator used.

Further, since this coating liquid contains a polymerizable unsaturated group, an alkoxysilyl group and a silanol group, it can be cured by heating with a hot air dryer, an IR dryer or the like.

After applying the resin composition of the present invention to the surface of the substrate by the coating method, the coated surface is irradiated with ultraviolet rays or the coated substrate is heated to obtain a laminate having excellent scratch resistance. be able to.

<Use>
Since the laminate of the present application is excellent in hard coat property and weather resistance, it can be particularly preferably used as various protective materials. For example, for building materials, housing equipment, transportation equipment such as automobiles, ships, aircraft, railroads, electronic materials, recording materials, optical materials, lighting, packaging materials, protection of outdoor installations, optical fibers. It is possible for coating, resin glass protection, etc.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but in the following, "part" and "%" are based on weight unless otherwise specified.

(Synthesis of compound B1)
Synthesis Example 1 UAS-1
To a four-necked flask, add 3-isocyanatepropyltriethoxysilane: KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) 247.4 parts by mass, dibutyltin dilaurate 0.2 parts by mass, and hydroquinone 0.2 parts by mass to make a uniform solution. And said. The flask was heated to an internal temperature of 60 ° C., and then 116.2 parts by mass of 2-hydroxyethyl acrylate was added dropwise over about 4 hours. After completion of the dropping, the mixture was heated at 70 ° C. for 5 hours, and the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy to obtain urethane (meth) silane acrylate: UAS-1.

Synthesis Example 2 UAS-2
To a four-necked flask, add 3-isocyanatepropyltriethoxysilane: KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) 247.4 parts by mass, dibutyltin dilaurate 0.2 parts by mass, and hydroquinone 0.2 parts by mass to make a uniform solution. And said. The flask was heated until the internal temperature reached 60 ° C., and then 144.2 parts by mass of 4-hydroxybutyl acrylate was added dropwise over about 4 hours. After completion of the dropping, the mixture was heated at 70 ° C. for 5 hours, and the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy to obtain urethane (meth) silane acrylate: UAS-2.

Synthesis Example 3 UAS-3
To a four-necked flask, add 3-isocyanatepropyltriethoxysilane: KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) 247.4 parts by mass, dibutyltin dilaurate 0.2 parts by mass, and hydroquinone 0.2 parts by mass to make a uniform solution. And said. The flask was heated until the internal temperature reached 60 ° C., and then 210.2 parts by mass of 8-hydroxyoctyl acrylate was added dropwise over about 4 hours. After completion of the dropping, the mixture was heated at 70 ° C. for 5 hours, and the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy to obtain urethane (meth) silane acrylate: UAS-3.

Synthesis Example 4 UAS-4
To a four-necked flask, add 3-isocyanatepropyltriethoxysilane: KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) 247.4 parts by mass, dibutyltin dilaurate 0.2 parts by mass, and hydroquinone 0.2 parts by mass to make a uniform solution. And said. The flask was heated until the internal temperature reached 60 ° C., and then 351 parts by mass of FA-2D (manufactured by Daicel Corporation) was added dropwise over about 4 hours. After completion of the dropping, the mixture was heated at 70 ° C. for 5 hours, and the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy to obtain urethane (meth) silane acrylate: UAS-4.

Synthesis Example 5 UAS-5
To a four-necked flask, 141.2 parts by mass of 2-isocyanate ethyl acrylate: Karenz AOI (manufactured by Showa Denko KK), 405.7 parts by mass of butyl isoacetate and 0.2 parts by mass of hydroquinone were added to prepare a uniform solution. The flask was heated until the internal temperature reached 60 ° C., and then 264.5 parts by mass of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise over about 4 hours. After completion of the dropping, the mixture was heated at 70 ° C. for 5 hours, and the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy to obtain urethane (meth) silane acrylate: UAS-5.

Synthesis Example 6 UAS-6
To a four-necked flask, add 3-isocyanatepropyltriethoxysilane: KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.) 247.4 parts by mass, dibutyltin dilaurate 0.2 parts by mass, and hydroquinone 0.2 parts by mass to make a uniform solution. And said. The flask was heated until the internal temperature reached 60 ° C., and then 497.3 parts by mass of pentaerythritol triacrylate (M-305 manufactured by Toagosei Co., Ltd.) was added dropwise over about 4 hours. After completion of the dropping, the mixture was heated at 70 ° C. for 5 hours, and the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy to obtain urethane (meth) silane acrylate: UAS-6.

<Synthesis of condensate>

Synthesis Example 7 Psi-1
UAS-06 216.0 g of Tris- (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Industry Co., Ltd .: KBM9659) 12.0 g (0.019 mol) synthesized in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. (0.29 mol), 140.8 g of propylene glycol monomethyl ether, phosphoric acid: 0.19 g of A-4 and 37.9 g of water were added, the temperature was raised to 80 ° C., and the mixture was stirred for 4 hours, and then the solid content was 80 wt. After removing the solvent to%, the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired condensate (Psi-1).

Synthesis Example 8 Psi-2
UAS-03 133. Synthesized with 12.0 g (0.019 mol) of trisu (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 9 g (0.29 mol), 177.1 g of propylene glycol monomethyl ether, phosphoric acid: 0.19 g of A-4 and 37.9 g of water were added, the temperature was raised to 80 ° C. and the mixture was stirred for 4 hours, and then the solid content was increased. After removing the solvent to 80 wt%, the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired condensate (Psi-2).

Synthesis Example 9 Psi-3
UAS-01 106. Synthesized with 12.0 g (0.019 mol) of trisu (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 4 g (0.29 mol), 135.8 g of propylene glycol monomethyl ether, phosphoric acid: 0.19 g of A-4 and 37.9 g of water were added, the temperature was raised to 80 ° C., and the mixture was stirred for 4 hours. After removing the solvent to 80 wt%, the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired condensate (Psi-3).

Synthesis Example 10 Psi-4
UAS-02 114. Synthesized with 12.0 g (0.019 mol) of trisu (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 6 g (0.29 mol), 148 g of propylene glycol monomethyl ether, phosphoric acid: 0.19 g of A-4 and 37.9 g of water were added, the temperature was raised to 80 ° C., and the mixture was stirred for 4 hours, and then the solid content was 80 wt%. After removing the solvent until it became, the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired condensate (Psi-2).

Synthesis Example 11 Psi-5
UAS-05 237 synthesized with 12.0 g (0.019 mol) of trisu (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 5 g (0.29 mol), 36 g of propylene glycol monomethyl ether, phosphoric acid: 0.19 g of A-4 and 37.9 g of water were added, the temperature was raised to 80 ° C., and the mixture was stirred for 4 hours, and then the solid content was 80 wt%. After removing the solvent until it became, the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired condensate (Psi-5).

Synthesis Example 12 Psi-6
UAS-02 114. Synthesized with 12.0 g (0.019 mol) of trisu (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Co., Ltd.) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 6 g (0.29 mol), tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-14) 130.1 g (0.61 mol), propylene glycol monomethyl ether 179.4 g, and phosphoric acid: A-4 0.65 g. After adding 127.4 g of water, raising the temperature to 80 ° C. and stirring for 4 hours, removing the solvent until the solid content reaches 80 wt%, the solid content becomes 40 wt% with propylene glycol monomethyl ether. The desired condensate (Psi-6) was obtained.

Synthesis Example 13 Psi-7
UAS-02 114. Synthesized with 12.0 g (0.019 mol) of trisu (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Co., Ltd.) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 6 g (0.29 mol), tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-14) 97.6 g (0.46 mol), propylene glycol monomethyl ether 165.2 g, and phosphoric acid: A-4 0.53 g. After adding 105.4 g of water, raising the temperature to 80 ° C. and stirring for 4 hours, removing the solvent until the solid content reaches 80 wt%, the solid content becomes 40 wt% with propylene glycol monomethyl ether. The desired condensate (Psi-7) was obtained.

Synthesis Example 14 Psi-8
UAS-02 114. Synthesized with 12.0 g (0.019 mol) of trisu (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Co., Ltd.) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 6 g (0.29 mol), tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-14) 65.0 g (0.30 mol), propylene glycol monomethyl ether 151.1 g, and phosphoric acid: A-4 0.42 g. 82.9 g of water was added, the temperature was raised to 80 ° C., and the mixture was stirred for 4 hours. Then, the solvent was removed until the solid content became 80 wt%, and then the solid content was 40 wt% with propylene glycol monomethyl ether. The desired condensate (Psi-8) was obtained.

Synthesis Example 15 Psi-9
UAS-02 114. Synthesized with 12.0 g (0.019 mol) of trisu (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Co., Ltd.) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 6 g (0.29 mol), tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-14) 12.2 g (0.06 mol), propylene glycol monomethyl ether 128.1 g, and phosphoric acid: A-4 0.23 g. After adding 46.4 g of water, raising the temperature to 80 ° C. and stirring for 4 hours, removing the solvent until the solid content becomes 80 wt%, the solid content becomes 40 wt% with propylene glycol monomethyl ether. The desired condensate (Psi-9) was obtained.

Synthesis Example 16 Psi-10
Trisoo (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Co., Ltd .: KBM9659) 20.0 g (0.032 mol) and 3-methacryloxypropyltrimethoxy in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. Add 121.2 g (0.49 mol) of silane (manufactured by Toray Dow Corning: XIAMETER OFS-6030 SILANE), 151.2 g of propylene glycol monomethyl ether, phosphoric acid: A-4 0.32 g and 63.2 g of water. After raising the temperature to 80 ° C. and stirring for 4 hours, the solvent was removed until the solid content became 80 wt%, and then adjusted with propylene glycol monomethyl ether so that the solid content became 40 wt%. A condensate (Psi-10) was obtained.

Synthesis Example 17 Psi-11
Tris- (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Co., Ltd .: KBM9659) 20.0 g (0.032 mol) and 3-methacryloxypropyltrimethoxy in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. Silane (manufactured by Toray Dow Corning: XIAMETER OFS-6030 SILANE) 121.2 g (0.49 mol), hand and tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-14) 20.32 g and propylene glycol monomethyl ether 170.9 g and phosphoric acid: A-4 0.39 g and 77.3 g of water were added, the temperature was raised to 80 ° C., the mixture was stirred for 4 hours, and then the solvent was removed until the solid content became 80 wt%. The solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired condensate (Psi-11).

Synthesis Example 18 Psi-12
UAS-04 176 synthesized with 12.0 g (0.019 mol) of trisu (trimethoxysilylpropyl) isocyanurate (KBM9659 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 8 g (0.29 mol), 402.1 g of propylene glycol monomethyl ether, phosphoric acid: 0.19 g of A-4 and 37.9 g of water were added, the temperature was raised to 80 ° C. and the mixture was stirred for 4 hours, and then the solid content was increased. After removing the solvent to 80 wt%, the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired condensate (Psi-12).

Synthesis Example 19 Psi-13
UAS-01 106.4 g (0.29 mol), propylene glycol monomethyl ether 128.8 g, phosphoric acid: A-4 0.19 g and water 37. Synthesized in a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer. After adding 9 g, raising the temperature to 80 ° C. and stirring for 4 hours, removing the solvent until the solid content reaches 80 wt%, and then adjusting the solid content to 40 wt% with propylene glycol monomethyl ether. The desired condensate (Psi-13) was obtained.

<Example 1>
(Preparation of composition)
100 parts by weight of the synthesized Psi-1 was added as a solid content, and 2 parts by weight of Irgure819 (BASF Corporation, photoinitiator) was added to the resin solid content and stirred, and then diluted with propylene glycol monomethyl ether. Composition 1 having a resin solid content of 40 parts by weight was obtained.

(Manufacturing of laminated body)
For the obtained composition 1, the laminate 1 was produced under the following conditions. Various tests were performed on the obtained laminate 1.

<Coating>
-Bar coater coating Bar coater coating is applied to the polycarbonate plate (Carboglass polish clear made by Asahi Glass, thickness 2 mm) so that the coating thickness after drying of the composition 1 prepared in Table 2-1 is about 10 to 20 μm. And dried in a dryer at 80 ° C. for 10 minutes.

<Curing>
For ultraviolet irradiation, a high-pressure mercury lamp manufactured by GS-YUASA Co., Ltd. is used, and the irradiation energy per pass is ^{200 mW / cm 2 in the UV-A region of UV POWER PUCK II manufactured by EIT.} 1000 mJ / cm ² and so as lamp output, lamp height, and to adjust the conveyor speed, to the irradiation curing reaction in one pass (total 1000 mJ / cm ^2), to obtain a laminate.

<Evaluation>
[Taber wear resistance test]
The surface of the laminate was rubbed by a method compliant with ASTM D1044 (wear wheel: CS-10F, load: 500 g, rotation speed: 500) in the Taber wear test, and the difference in cloudiness value from the initial state, that is, haze. Value change ΔH (%) is measured. The smaller the difference, the higher the wear resistance, and ΔHaze ≦ 4.0 was set as the passing value.

[Haze value]
The light transmittance of the test piece is measured using a haze meter and calculated by the following formula (unit:%).

(Moisture resistance test)
After standing at 50 ° C. and 95% for 360 hours in a bleaching constant temperature and humidity chamber, each of the above samples was returned to room temperature, and changes in the surface layer of the laminate were visually confirmed.

⊚: No cloudiness occurred.
〇: There was some cloudiness.
×: White turbidity was clearly generated. ・ After standing at 50 ° C. and 95% for 360 hours in a close contact constant temperature and humidity chamber, the above samples were returned to room temperature.
A 100-square grid adhesion test was carried out.
◎: Adhesion of 100 squares 〇: Adhesion of 50 to 99 squares ×: Adhesion of 0 to 50 squares

(Cold heat resistance test)
・ After repeating the crack cycle, return each of the above samples to room temperature, visually check the change in the surface layer of the laminated body, and allow it to stand at -30 ° C for 1 hour and then at 110 ° C for 1 hour using a thermal test device. bottom. This was carried out for 100 cycles.
⊚: No cracks occurred 〇: Cracks were slightly generated ×: Cracks were clearly generated.

-In a close contact cold test device, the mixture was allowed to stand at -30 ° C for 1 hour and then at 110 ° C for 1 hour. After repeating this for 100 cycles, each of the above samples was returned to room temperature, and a 100-square grid adhesion test was carried out.
◎: Adhesion of 100 squares 〇: Adhesion of 50 to 99 squares ×: Adhesion of 0 to 50 squares

(SUV accelerated weathering test)
Using Iwasaki Electric's super-accelerated weather resistance tester Super UV Tester (SUV), 4-hour irradiation panel temperature 63 ° C humidity 90%) and 4-hour condensation (black panel temperature 30 ° C humidity 95%) (irradiation intensity 100 mW) , Black panel temperature 63 ° C., humidity 70%) and darkness for 4 hours (black 12 hours was set as one cycle, and 60 cycle evaluation was performed.

(crack)
◯: No cracks on the surface ×: Cracks on the surface

<Examples 2 to 20>
In Example 1, coating agents 2 to 12 were obtained in the same manner except that the compounding ratio was changed to the compounding ratios shown in Tables 1-1 and 1-2. For each of the obtained compositions, laminated bodies 2 to 12 were prepared in the same manner as in Example 1, and various evaluations were performed.

PGM-ST (manufactured by Nissan Chemical Industries, Ltd.): Unmodified colloidal silica
MEK-AC (manufactured by Nissan Chemical Industries, Ltd.): 3-methacryloyl-modified colloidal silica Irg819 (manufactured by BASF: Irgacure819)

<Comparative Examples 1 to 4>
Comparative coating agents 1 to 4 were obtained in the same manner as in Example 1 except that the compounding was changed to the compounding ratio shown in Table 2. For each of the obtained compositions, comparative laminates 1 to 4 were prepared in the same manner as in Example 1, and various evaluations were performed.

Since the coating agent of the present invention can obtain a cured product having excellent wear resistance, weather resistance, cold heat resistance, and moisture heat resistance, it is possible to produce a laminate having excellent hard coat properties.

Claims (9)

It contains a structure (A) represented by the following formula (1), a structure (B) represented by the following formula (3), and a silane condensate having either or both of urethane and urea bonds. A coating agent characterized by.

... (1)
(In the formula, X _{1 to} X ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a group represented by the formula (2), _{and at least one of X 1 to} X ₃ is the formula (2). ) Is the group represented by.

... (2)
(In the formula, R ¹ represents an alkyl group having 1 to 15 carbon atoms.
Y ₁ is a bonding group having one or more of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond, and n 1 represents an integer of 1 to 3. )))

... (3)
(In the formula, R ² indicates an alkyl group having 1 to 15 carbon atoms, and R ³ indicates a hydrogen atom or a methyl group.
Y ₂ is a bonding group having one or more of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond, n2 represents an integer of 1-3, and n3 represents an integer of 1-3. show. (In the formula, the oxygen atom bonded to the Si atom may be shared with the oxygen atom bonded to the Si atom in the above formula (1).) The coating agent according to claim 1, wherein _{any one of Y 1} and / or Y ₂ has a structure represented by the following formula (4).

... (4)
(In the formula, R ^{4 to} R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Z indicates a bonding group having a urea or urethane bond, n3 indicates a number of 1 to 3, l indicates a number of 1 to 10, and m indicates a number of 1 to 10. The coating agent according to claim 1 or 2, wherein the silane condensate contains a structure (C) represented by the following formula (5).

... (5) It contains the compound (A1) represented by the formula (6) and the compound (B1) represented by the formula (8), and at least one of the compound (A1) and the compound (B1) is at least one urethane or urea bond. A coating agent containing a condensate of a composition comprising one.

... (6)
(Wherein, X ₄ to X ₆ are each independently a hydrogen atom, an alkyl group or a group represented by the formula (7) of 1 to 15 carbon atoms, at least one of the formula X ₄ to X ₆ (7 ) Is the group represented by.

・ ・ ・ ・ (7)
Y ₃ is a bonding group having one or more of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond, and in the formula, R ¹⁰ represents an organic group having 1 to 15 carbon atoms, and R ¹¹ represents an organic group or a hydrogen atom having 1 to 15 carbon atoms, and n4 represents an integer of 1 to 3 carbon atoms.

... (8)
(In the formula, R ¹² and R ¹³ indicate an alkyl group or a hydrogen atom having 1 to 15 carbon atoms, and R ¹⁴ indicates a hydrogen atom or a methyl group.
Y ₄ represents an alkyl group having 1 to 10 carbon atoms, a linking group having any one or more of the urea bond and urethane bond, n5 is an integer of 1 to 3, a is an integer of from 1 to 3 n6 show. ) The coating agent according to claim 4, wherein _{any one of Y 3} and / or Y ₄ has a structure represented by the following formula (9).

... (9)
(Wherein, R ¹⁵ to R ¹⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Z is represents a bonding group having a urea or urethane bond, n7 is a number from 1 to 3 , L indicates a number from 1 to 10, and m indicates a number from 1 to 10.) The coating agent according to claim 4 or 5, which is a composition containing alkoxysilane. The coating agent according to any one of claims 1 to 6, which is for a hard coat. A coating film obtained by curing the coating agent according to any one of claims 1 to 7. A laminate having the coating film according to claim 8.