WO2020130072A1 - Coating agent, coating film, and laminate - Google Patents

Abstract

The present invention provides a coating agent characterized by containing a silane condensate that has a structure (A) represented by formula (1), a structure (B) represented by formula (3), and one or both of a urethane bond and a urea bond.　The present invention also provides a coating film obtained by curing the coating agent. The present invention also provides a laminate having the coating film.

Description

Coating agent, coating film and laminate

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 an alternative to glass is increasing. In particular, polycarbonate resins and the like are widely used because of their excellent heat resistance, impact resistance, and transparency. However, since polycarbonate resins and the like are inferior in scratch resistance and weather resistance to glass, a hard coat material for protecting the surface thereof has been proposed.

Generally, as a means for improving wear resistance, a hard coat layer requires high hardness, and many coating materials using an organosiloxane composition have been proposed. However, when the hardness is increased, the obtained film becomes brittle, and further, the adhesion to the resin base material is reduced and the difference in the behavior of the environmental dimensional change from the resin base material becomes large, and 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 adhesion, but there is a drawback that abrasion resistance decreases, and particularly with a hard coat for automobile windows that requires visibility. It is insufficient to satisfy the wear resistance, adhesion and weather resistance equivalent to those of glass such as resin substrates (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. The hard coat layer is called abrasion resistance and weather resistance, and the primer layer is called weather resistance and adhesion. Techniques with different functions have been proposed.

For example, an acrylic resin thermosetting film, an organosiloxane resin thermosetting film, and a silicon oxide film deposited by plasma-induced chemical vapor deposition (CVD) using an organic silicon compound as a raw material on the surface of a polycarbonate substrate. Is proposed. However, although this laminate has improved weather resistance and abrasion resistance, it requires a dry process step such as a vacuum chamber for depositing a silicon oxide film, resulting in a high process cost and a large load for general-purpose diffusion. Can be said. 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 since the curing requires a high temperature and a long time, the productivity is poor and the abrasion resistance is not sufficiently satisfactory.
In order to solve the above problems, Patent Document 3 proposes a coating agent capable of forming a film by a wet process and protecting the surface of an organic resin substrate, which enables production in a short time by ultraviolet curing. As a result of examination by the present inventor, abrasion resistance, wet heat resistance, cold heat resistance, and weather resistance are not satisfied.

Japanese Patent Publication No. 3-45094 Japanese Patent No. 4462421 Japanese Patent Laid-Open No. 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, and cold/heat resistance as well as excellent wet heat resistance. Another object is to provide a laminate having the coating film.

As a result of intensive studies by the present inventors, it is possible to solve the above problems 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 is
Containing a structure (A) represented by the following formula (1), a structure (B) represented by the following formula (3), and a silane condensate having one or both of urethane and urea bonds. To provide a coating agent.

...(1)

(In the formula, each of X ₁ to X ₃ independently represents 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 represented by the formula (2 ) Is a 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 n1 is an integer of 1 to 3. ))

...(3)

(In the formula, R ² represents an alkyl group having 1 to 15 carbon atoms, R ³ represents 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 is an integer of 1 to 3, and n3 is an integer of 1 to 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 in which 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 represents a bonding group having a urea or urethane bond, n3 represents a number of 1 to 3, l represents a number of 1 to 10, and m represents a number of 1 to 10.)

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

...(5)

Further, the present invention comprises 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 Provided is a coating agent containing a condensate of a composition having at least one urethane or urea bond.

...(6)

(In the formula, X ₄ to X ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a group represented by the formula (6), and at least one of X ₄ to X ₆ is represented by the formula (7 ) Is a 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, wherein R ¹⁰ represents an organic group having 1 to 15 carbon atoms, and R 3 ¹¹ represents an alkyl group having 1 to 15 carbon atoms or a hydrogen atom. n4 represents an integer of 1 to 3.

...(8)

(In the formula, R ¹² and R ¹³ represent an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, and R ¹⁴ represents a hydrogen atom or a methyl group,
Y ₄ is a bonding group having at least one of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond, n5 is an integer of 1 to 3, and n6 is an integer of 1 to 3. Show. )

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

...(9)

(In the formula, R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and Z Represents a bonding group having a urea or urethane bond, n7 represents a number of 1 to 3, l represents a number of 1 to 10, and m represents 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 provide a coating film having excellent wear resistance, weather resistance, and cold/heat resistance, particularly long-term weather resistance. Furthermore, since it is excellent in moist heat resistance and moldability, it can be suitably used for hard coats, especially for outdoor use.

The present invention provides a silane condensate having a structure (A) represented by the following formula (1), a structure (B) represented by the following formula (3), and either or both of a urethane bond and a urea bond. A coating agent comprising:

...(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, 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)

(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, n1 represents an integer of 1 to 3.))

...(3)

(In the formula, R ² represents an alkyl group having 1 to 15 carbon atoms, R ³ represents a hydrogen atom or a methyl group, and Y ₂ represents one of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond. In the formula (1), 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 in ).)

The coating agent of the present invention is a condensate having an isocyanuric ring structure and a (meth)acryloyl group, and is characterized by having a urea bond or a urethane bond in the condensate. By having a urea bond or a urethane bond in the condensate, the wet heat resistance of the obtained coating film is improved. In addition, the action of the urea bond or the urethane bond also improves the moldability and the resistance to cold and heat. The urea bond and the urethane bond may have one or more of any one type in the condensate, and may have one or more of two types respectively.

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

In the condensate, a preferred structure is a coating agent, wherein any one of Y ₁ and/or Y ₂ is 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 represents a bonding group having a urea or urethane bond, n3 represents a number of 1 to 3, l represents a number of 1 to 10, and m represents a number of 1 to 10.

R ⁴ to R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom. .. Further, n3 is a number of 1 to 3, but is preferably 1. The above l is a number of 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Further, m is a number of 1 to 10, preferably 1 to 8, and more preferably 1 to 6.

<Structure (A)>
Structure A of the present invention is a structure having an isocyanuric 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), at least one of which is represented by the formula (2). It is a group that is
In the formula (1), preferably at least two of X ₁ to X ₃ are groups represented by the formula (2), and more preferably all of X ₁ to X ₃ are represented by the formula (2). And n1 is preferably selected from 2 or 3.

<Structure B>
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. It is preferable.

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

...(5)

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

...(6)

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

...(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 having 1 to 15 carbon atoms or a hydrogen atom.

...(8)

(In the formula, R ¹² and R ¹³ represent an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, R ¹⁴ represents a hydrogen atom or a methyl group, Y ₄ represents an alkyl group having 1 to 10 carbon atoms, a urea bond and A bonding group having any one or a plurality of urethane bonds, wherein 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 is a structure represented by the following formula (9).

...(9)

(In the formula, R ¹⁵ to R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 15 carbon atoms; Represents a bonding group having a urea or urethane bond, n7 represents a number of 1 to 3, l represents a number of 1 to 10, and m represents a number of 1 to 10.)

<Compound (A1)>
In the compound (A1) represented by formula (6), at least one of X ₄ to X ₆ is a group represented by formula (7). _Preferably, a group represented by at least 2 Exemplary ethynylphenylbiadamantane derivatives of X 4 ~ _{X 6} (7), more preferably when both are three _X 4 ~ _{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 structure having a urea bond or a urethane bond and a compound having a structure having no urea bond or a urethane bond.
Specific examples of the compound 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- Trimethoxysilylpropyl) isocyanurate, 1-glycidylmethyl-3,5-bis(3-trimethoxysilylpropyl) isocyanurate, 1,3-bis(glycidylmethyl)-5-(3-trimethoxysilylpropyl) isocyanate Nulate, 1-glycidylmethyl-3-(2-propen-1-yl)-5-(3-triethoxysilylpropyl) isocyanurate, 1,3-dimethyl-5-(3-triethoxysilylpropyl) isocyanurate Etc. Preferred examples 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 structure having a urea bond, it can also be obtained by reacting an isocyanurate compound having an isocyanate group with an alkoxysilane compound having an amino group. it can.

As the isocyanurate compound having an isocyanate group, 1,6 hexane diisocyanate isocyanurate, 1,5 pentane diisocyanate isocyanurate, isophorone diisocyanate isocyanurate, dicyclohexylmethane 4,4-diisocyanate isocyanurate 1, Examples thereof include an isocyanurate body of 3-bisisocyanate methylcyclohexane and an isocyanurate body of 1,4-bisisocyanate methylcyclohexane. Preferably, it is an isocyanurate body of 1,5 pentane diisocyanate or an isocyanurate body of 1,6 hexane diisocyanate.

Examples of the alkoxysilane compound having an amino group include 3-aminopropyltrialkoxysilane, N-2-(aminoethyl)3-aminopropyltrimethoxysilane, 8-aminooctyltrialkoxysilane, 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, and more preferably 1.

It is preferable that either Y ₃ or Y ₄ has a structure represented by the following formula (9). In formula (9), R ¹⁵ to R ¹⁹ are preferably methyl groups or hydrogen groups, and more preferably hydrogen groups. Further, n7 is a number of 1 to 3, but is preferably 1.
The above l is a number of 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Further, 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 structure having a urea bond or a urethane bond and a compound having a structure having no urea bond or a urethane bond.
Examples of compounds having no urea bond or urethane bond are 3-propyl(meth)acryloyltrimethoxysilane, 3-propyl(meth)acryloyltriethoxysilane, 8-octyl(meth)acryloyltrimethoxysilane, 8- 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. Are listed.

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

Examples of the silane compound having an isocyanate group include 3-isocyanatepropyltriethoxysilane, 5-isocyanatopentyltriethoxysilane, 6-isocyanatehexyltriethoxysilane, and 8-isocyanateoctyltriethoxysilane. Of these, 3-isocyanatopropyltriethoxysilane 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-hydroxybutyl (meth)acrylate. 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 (Meth)acrylate, 1-ethyl-3-hydroxy-propyl (meth)acrylate, 3-hydroxy-hexyl (meth)acrylate, 3-hydroxy-2-propylpropyl (meth)acrylate, 3-hydroxy-1-propylpropyl (Meth)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 acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, and a reaction product with an amino-base-containing (meth)acrylate. Further, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy (meth)acrylate (for example, trade name "Plaxel" manufactured by Daicel Chemical Industries, Ltd.), phthalic acid and propylene. Examples thereof include mono(meth)acrylate of polyester diol obtained from glycol. Among them, 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. You can 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 have an amino group such as 3-aminopropyltriethoxysilane, 8-aminooctyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 8-aminooctylmethyldiethoxysilane and the like. Alkoxysilane and the like. Of these, 3-aminopropyltriethoxylane is preferable.

Examples of the (meth)acrylate compound having an isocyanate group include 2-isocyanate ethyl (meth)acrylate, 3-isocyanate propyl (meth)acrylate, 2-isocyanate propyl (meth)acrylate, 4-isocyanate butyl (meth)acrylate, 6 -Isocyanate hexyl (meth)acrylate, 8-isocyanate octyl (meth)acrylate, 10-isocyanate decane (meth)acrylate and the like. Among them, 2-isocyanate ethyl (meth)acrylate, 3-isocyanate propyl (meth)acrylate, 2-isocyanate propyl (meth)acrylate and 4-isocyanate butyl (meth)acrylate are preferable.

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

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 is because when it is in this range, it is excellent from the viewpoint of heat and humidity resistance. More preferably, it is 1:6 to 1:20.

In compound (A1) and compound (B1), at least one of Y _{3 and} Y ₄ in the formula is preferably a bonding group having a urea bond or a urethane bond. This is because when the portion has a urea bond or a urethane bond, the resulting condensate is excellent in wet heat resistance and moldability. Preferred is a case where any of Y ₃ and/or Y ₄ has a structure represented by the following formula (9).

...(9)

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

R ¹⁵ to R ¹⁸ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably a hydrogen atom. .. Further, n7 is a number of 1 to 3, but is preferably 1. The above l is a number of 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Further, 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 be introduced by condensing the compound (A1) and the compound (B1), but preferably, alkoxysilane is blended and cocondensed.

The alkoxysilane is not particularly limited, but dialkoxysilane, trialkoxysilane and tetraalkoxysilane are preferable. Among them, trialkoxysilane and/or tetraalkoxysilane are preferable.

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-glycidylpropyltrimethoxysilane, 3-glycidylpropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, N-2-(aminoethyl)3-aminopropyltrimethoxysilane, N-2-(aminoethyl)3 -Aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like can be mentioned.

Specific examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, isobutyl silicate, n-butyl silicate, 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 an alkoxysilane, the compounding amount is preferably 200 mol% or less based on the total molar amount of (A1) and (B1). It is more preferably 150 mol% or less.

The composition of the present invention may contain other formulations.
Other compounds 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, Flow control agent, coupling agent, dye, leveling agent, rheology control agent, UV absorber, antioxidant, plasticizer, etc., in addition to the silane condensate having the above structure, other silane condensate, for example, used for condensation And a single condensate or a complex condensate of the respective silane compounds.

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

As the method of hydrolysis, the solution is preferably hydrolyzed with acidic water having a pH of 1 to 7. This pH adjustment includes hydrochloric acid, nitric acid, 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 a catalyst. The amount of the above acid or acid catalyst used is 0.0001 to 20% by weight based on the product.

The presence of water is required in the hydrolysis reaction. The amount of water may be at least an amount sufficient to hydrolyze (a part of) the hydrolyzable groups in the silane compound or silicate compound, and may be 0 of the theoretical amount (mol) of the number of hydrolyzable groups. It is preferably an amount corresponding to 0.5 to 5.0 times mol. Also, if the acidic catalyst is added as an aqueous solution, the water is included in 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 the drying efficiency.

ㆍDehydration condensation reaction of the silanol groups generated at the same time as hydrolysis occurs, resulting in a siloxane resin. The temperature at which this condensation is carried out is room temperature or under heating at 120° C. or lower, 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, resulting in low productivity, 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 above hydrolysis and condensation and the molecular weight of the resulting resin. 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, Examples of diacetone alcohol and ester include ethyl acetate, methyl acetate, butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, butyl lactate, and ethers. Isopropyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycol ester type ethylene glycol monoethyl ether acetate, methoxypropyl acetate, butyl carbitol acetate, Ethyl carbitol acetate, glycol ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, butyl diglycol, methyl triglycol, 1-methoxy-2-propanol, propylene glycol monobutyl ether, 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, hydrogencarbonates include benzene, toluene and xylene. Can be mentioned. These organic solvents may be used alone or in combination of two or more.

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

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

Also, the coating agent of the present invention may contain other compound 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 control agents, cups. A ring agent, a dye, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant, a plasticizer, etc. may be added.

The reactive compounds include monofunctional (meth)acrylate and polyfunctional (meth)acrylate.

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

As the polyfunctional (meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di( (Meth)acrylate, glycerol tri(meth)acrylate modified by ethylene oxide, glycerol tri(meth)acrylate modified by propylene oxide, trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate modified by hydroxypivalic acid , Trimethylolpropane tri(meth)acrylate modified with ethylene oxide, trimethylolpropane tri(meth)acrylate modified with propylene oxide, phosphoric acid 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 (Meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, dipentaerythritol hexa modified with ethylene oxide (Meth)acrylate, dipentaerythritol hexa(meth)acrylate modified with propylene oxide, urethane (meth)acrylate compound obtained by reacting an isocyanate compound with an alcohol compound, polyhydric alcohol and (meth)acrylic acid, and polyfunctionality Examples thereof include a polyester (meth)acrylate compound synthesized by a condensation reaction with a carboxylic acid, an epoxy (meth)acrylate compound synthesized by an addition reaction of a bisphenol type epoxy resin or a novolac type epoxy resin and (meth)acrylic acid. ..

Examples of the organic solvent include ester solvents, ketone solvents, ether solvents, aliphatic solvents, aromatic solvents, and alcohol solvents.
Specifically, the ester-based solvent is ethyl acetate-, propyl acetate, butyl acetate, the ketone-based solvent is acetone, 2-butanone, methyl ethyl-ketone, methyl isobutyl ketone, etc., and the ether-based 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. ..

Alternatively, a liquid organic polymer may be used to adjust the viscosity. The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples thereof include a carboxyl group-containing polymer modified product (Floren G-900, NC-500: Kyoeisha), an acrylic polymer (Floren WK-20: Kyoeisha), Examples include amine salts of specially modified phosphoric acid esters (HIPLAAD ED-251: Kusumoto Kasei), modified acrylic block copolymers (DISPERBYK2000; Big Chemie), and the like.

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

A thermosetting resin is a resin that has the property of being substantially insoluble and infusible when cured by heating or by means such as radiation or a catalyst. As a specific example thereof, the thermosetting resin is a resin having the property of being substantially insoluble and infusible when it is cured by heating or means such as 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, xylene. Examples thereof include resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, and styrene/maleic anhydride (SMA) resins. These thermosetting resins can be used alone or in combination of two or more.

-Thermoplastic resin refers to 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, 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, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndyne Examples include tactic 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 may 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 powdery silica fine particles include, for example, Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd. E220A manufactured by Nippon Silica Industry Co., Ltd. , E220, SYLYSIA470 manufactured by Fuji Silysia Ltd., SG flakes manufactured by Nippon Sheet Glass Co., Ltd., and the like.
Examples of commercially available colloidal silica include methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, MEK-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned.

Reactive silica may be used as the silica. 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.
Examples of commercially available powdery silica modified with a compound having a (meth)acryloyl group include Aerosil RM50 and R711 manufactured by Nippon Aerosil Co., Ltd., and commercially available colloidal silica modified with a compound having a (meth)acryloyl group. Examples include MIBK-SD, MIBK-SD-L, MIBK-AC-2140Z, MEK-AC-2140Z manufactured by Nissan Chemical Industries, Ltd. Further, silica modified with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane and then subjected to an addition reaction with acrylic acid, or a compound having 3-isocyanatepropyltriethoxysilane and a hydroxyl group and a (meth)acryloyl group is urethane. The silica modified by the chemical reaction can also be mentioned as the reactive silica.

The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregular shapes can be used. For example, as commercially available hollow silica fine particles, Silinax manufactured by Nittetsu Mining Co., Ltd. can be used.
The primary particle diameter 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 blending amount of silica 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 particulate, plate-shaped, and fibrous fillers.

For example, those having excellent heat resistance are alumina, magnesia, titania, zirconia, etc.; those having excellent heat conduction are boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.; As a material having excellent conductivity, a metal filler and/or a metal-coated filler using a simple metal or an alloy (for example, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); a barrier. Examples of excellent properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite and smectite, and potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate. , Zinc oxide, magnesium hydroxide; barium titanate, zirconia oxide, titanium oxide, etc. having a high refractive index; titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus showing a photocatalytic property. , Carbon, sulfur, terium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, and other photocatalytic metals, composites of the above metals, oxides thereof, etc.; Metals such as alumina, zirconia, and magnesium oxide, and their composites and oxides; those having excellent conductivity, such as metals such as silver and copper, tin oxide, indium oxide, etc.; those having excellent ultraviolet shielding, Examples include titanium oxide and zinc oxide.
These inorganic fine particles may be appropriately selected depending on the application and may be used alone or in combination of two or more kinds. Further, since the above-mentioned inorganic fine particles have various characteristics in addition to the characteristics given in the examples, they may be appropriately selected according to the application.

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

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

The blending amount of the filler is preferably 3 to 60 parts by weight when the solid content of the total amount of the compound having the (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. Any known photopolymerization initiator 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-methylpropan-1-one, 4 Examples include -(2-hydroxy-ethoxy)phenyl-(2-hydroxy-2-propyl)ketone. Examples of the benzyl ketals include 1-hydroxy-cyclohexyl-phenyl ketone and benzyl dimethyl ketal. Examples of the benzophenones include benzophenone and methyl o-benzoylbenzoate. Examples of the benzoins and the like 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 kinds. 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 incorporated 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 improving the leveling property at the time of application, the slip property of the cured film and the scratch resistance. As the surface modifier, various additives that are commercially available under the names such as a surface conditioner, a leveling agent, a slipperiness imparting agent, and an antifouling agent can be used. Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. 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, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, Examples thereof include fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain. One or more of these may be used. For the purpose of increasing the sustainability of slipperiness, those containing a (meth)acryloyl group in the molecule may be used. Specific surface modifiers include EBECRYL350 (Daicel 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.), Megafac RS-75 (DIC Corporation), Megafac RS- 76-E (DIC Corporation), MegaFac RS-72-K (DIC Corporation), MegaFac RS-76-NS (DIC Corporation), MegaFac RS-90 (DIC Corporation), MegaFac RS- 91 (DIC Corporation), MegaFac RS-55 (DIC Corporation), Optool DAC-HP (Daikin Industry Co., Ltd.), ZX-058-A (T&K TOKA Corporation), ZX-201 (T&K TOKA Corporation) , ZX-202 (T&K TOKA Corporation), ZX-212 (T&K TOKA Corporation), ZX-214-A (T&K TOKA Corporation), X-22-164AS (Shin-Etsu Chemical Co., Ltd.), X-22- 164A (Shin-Etsu Chemical Co., Ltd.), X-22-164B (Shin-Etsu Chemical Co., Ltd.), X-22-164C (Shin-Etsu Chemical Co., Ltd.), X-22-164E (Shin-Etsu Chemical Co., Ltd.), X- 22-174DX (Shin-Etsu Chemical Co., Ltd.) and the like.

In the coating agent of the present invention, the compounding amount of the silane condensate of the present invention is preferably 10 to 100 wt% with respect to the total amount of the nonvolatile 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 coating the base material with the coating agent of the present invention and curing it, a laminate having a coating film can be obtained.

The base material in the laminate is not particularly limited, and examples thereof include polyolefins such as polyethylene, polypropylene and ethylene-propylene copolymer; polyesters such as polyethylene isophthalate, polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate; nylon 1 Polyamides such as nylon, nylon 11, nylon 6, nylon 66, nylon MX-D; polystyrene, styrene-butadiene block copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer (ABS resin), etc. Styrene-based polymers; acrylic-based polymers such as polymethylmethacrylate, methylmethacrylate/ethylacrylate copolymer, polycarbonates and the like can be used. The plastic substrate 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, the plastic substrate, if necessary, within the range not impairing the effects of the present invention, if necessary, known antistatic agents, antifogging agents, antiblocking agents, ultraviolet absorbers, antioxidants, light stabilizers, Known additives such as a crystal nucleating agent and a lubricant may be included.

The plastic substrate may be subjected to a known surface treatment on the surface of the substrate in order to further improve the adhesion with the resin composition of the present invention. Examples of such surface treatment include corona discharge treatment. , Plasma treatment, flame 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 shape, a plate shape, a spherical shape, a film shape or a large structure, or an assembly or a molded product having a complicated shape. The surface of the base material may be previously coated with an undercoat paint or the like, and the resin composition of the present invention can be applied even if the coated portion is deteriorated.

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

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

ㆍActive energy ray curing means curing by irradiating the coated product with active energy rays. Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron rays, α rays, β rays, and γ rays. Among these, ultraviolet rays (UV) are particularly preferable in terms of curability and convenience. As the light used for ultraviolet curing, 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, etc. can be used. By using these, and irradiating the coating surface of the coating product with ultraviolet rays having a wavelength of about 180 to 400 nm, the coating film can be cured to form a cured product layer to obtain a laminate. The irradiation amount of ultraviolet rays is appropriately selected depending on the type and amount of the photopolymerization initiator used.

Also, since the 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 coating the resin composition of the present invention on 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 has excellent hard coat properties and weather resistance, it can be particularly suitably used as various protective materials. For example, for building materials, housing equipment, transportation equipment such as automobiles, ships, aircraft and railways, electronic materials, recording materials, optical materials, lighting, packaging materials, protection of outdoor installations, optical fibers. It can be used for coating and protection of resin glass.

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

(Synthesis of Compound B1)
Synthesis Example 1 UAS-1
3-isocyanatopropyltriethoxysilane: 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 are added to a four-necked flask to obtain a uniform solution. And The inner temperature of the flask was heated to 60° C., and then 116.2 parts by mass of 2-hydroxyethyl acrylate was added dropwise over about 4 hours. After completion of dropping, the mixture was heated at 70° C. for 5 hours, the disappearance of isocyanate groups was confirmed by infrared absorption spectrum, and urethane (meth)silane acrylate:UAS-1 was obtained.

Synthesis Example 2 UAS-2
3-isocyanatopropyltriethoxysilane: 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 are added to a four-necked flask to obtain a uniform solution. And The inner temperature of the flask was heated to 60° C., and then 144.2 parts by mass of 4-hydroxybutyl acrylate was added dropwise over about 4 hours. After completion of dropping, the mixture was heated at 70° C. for 5 hours, the disappearance of isocyanate groups was confirmed by infrared absorption spectrum, and urethane (meth)silane acrylate:UAS-2 was obtained.

Synthesis Example 3 UAS-3
3-isocyanatopropyltriethoxysilane: 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 are added to a four-necked flask to obtain a uniform solution. And The inner temperature of the flask was heated to 60° C., and then 210.2 parts by mass of 8-hydroxyoctyl acrylate was added dropwise over about 4 hours. After completion of dropping, the mixture was heated at 70° C. for 5 hours, the disappearance of isocyanate groups was confirmed by infrared absorption spectrum, and urethane (meth)silane acrylate:UAS-3 was obtained.

Synthesis Example 4 UAS-4
3-isocyanatopropyltriethoxysilane: 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 are added to a four-necked flask to obtain a uniform solution. And The inner temperature of the flask was heated to 60° C., and then 351 parts by mass of FA-2D (manufactured by Daicel Corp.) was added dropwise over about 4 hours. After the completion of dropping, the mixture was heated at 70° C. for 5 hours, the disappearance of isocyanate groups was confirmed by infrared absorption spectrum, and urethane (meth)silane acrylate:UAS-4 was obtained.

Synthesis Example 5 UAS-5
To a four-necked flask, 141.2 parts by mass of 2-isocyanate ethyl acrylate: Karens 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 inner temperature of the flask was heated to 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, the disappearance of isocyanate groups was confirmed by infrared absorption spectrum, and urethane (meth)silane acrylate:UAS-5 was obtained.

Synthesis Example 6 UAS-6
3-isocyanatopropyltriethoxysilane: 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 are added to a four-necked flask to obtain a uniform solution. And The inner temperature of the flask was heated to 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 dropping, the mixture was heated at 70° C. for 5 hours, the disappearance of isocyanate groups was confirmed by infrared absorption spectrum, and urethane (meth)silane acrylate:UAS-6 was obtained.

<Synthesis of condensate>

Synthesis Example 7 Psi-1
12.0 g (0.019 mol) of tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) was synthesized in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. UAS-06 216.0 g synthesized (0.29 mol), 140.8 g of propylene glycol monomethyl ether, 0.19 g of phosphoric acid: 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, then the solid content was 80 wt. The solvent was removed until the content of the solid content was adjusted to 40%, and 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 tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 9 g (0.29 mol), propylene glycol monomethyl ether (177.1 g), phosphoric acid: A-4 (0.19 g) and water (37.9 g) were added, and the mixture was heated to 80° C. and stirred for 4 hours. The solvent was removed to 80 wt%, and 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. was synthesized with 12.0 g (0.019 mol) of tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 4 g (0.29 mol), propylene glycol monomethyl ether (135.8 g), phosphoric acid: A-4 (0.19 g) and water (37.9 g) were added, the temperature was raised to 80° C., and the mixture was stirred for 4 hours. The solvent was removed to 80 wt% and 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 tris-(trimethoxysilylpropyl)isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) 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, 0.19 g of phosphoric acid: 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, then the solid content was 80 wt %. After the solvent was removed 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 tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) 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, 0.19 g of phosphoric acid: 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. Then, the solid content was 80 wt %. After the solvent was removed 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 tris-(trimethoxysilylpropyl)isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 6 g (0.29 mol), tetraethoxysilane (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 and heating to 80° C. and stirring for 4 hours, the solvent was removed until the solid content became 80 wt %, and then the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether. The condensate (Psi-6), which was the target substance, was obtained.

Synthesis Example 13 Psi-7
UAS-02 114.synthesized with 12.0 g (0.019 mol) of tris-(trimethoxysilylpropyl)isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) 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 and heating to 80° C. and stirring for 4 hours, the solvent was removed until the solid content became 80 wt %, and then the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether. After that, the desired condensate (Psi-7) was obtained.

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

Synthesis Example 15 Psi-9
UAS-02 114.synthesized with 12.0 g (0.019 mol) of tris-(trimethoxysilylpropyl)isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 6 g (0.29 mol), tetraethoxysilane (KBE-14 manufactured by Shin-Etsu Chemical Co., Ltd.) 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 and heating to 80° C. and stirring for 4 hours, the solvent was removed until the solid content became 80 wt %, and then the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether. After that, the desired condensate (Psi-9) was obtained.

Synthesis Example 16 Psi-10
20.0 g (0.032 mol) of tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) and 3-methacryloxypropyltrimethoxy were placed in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer. 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, 0.32 g of phosphoric acid: A-4 and 63.2 g of water were added. After heating to 80° C. and stirring for 4 hours, the solvent was removed until the solid content became 80 wt %, and the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether to obtain the desired product. A certain condensate (Psi-10) was obtained.

Synthesis Example 17 Psi-11
20.0 g (0.032 mol) of tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) and 3-methacryloxypropyltrimethoxy were placed 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: 0.39 g of A-4 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 %. It was adjusted with propylene glycol monomethyl ether so that the solid content was 40 wt %, to obtain a condensate (Psi-11) as a target.

Synthesis Example 18 Psi-12
UAS-04 176. Synthesized with 12.0 g (0.019 mol) of tris-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM9659) 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, 0.19 g of phosphoric acid: 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. The solvent was removed to 80 wt%, and 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) synthesized in a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, propylene glycol monomethyl ether 128.8 g, phosphoric acid: A-4 0.19 g, and water 37. After adding 9 g and heating to 80° C. and stirring for 4 hours, the solvent was removed until the solid content became 80 wt %, and the solid content was adjusted to 40 wt% with propylene glycol monomethyl ether. As a result, the desired condensate (Psi-13) was obtained.

<Example 1>
(Preparation of composition)
100 parts by weight of the synthesized Psi-1 as a solid content, 2 parts by weight of Irgcure819 (BASF Corporation, photoinitiator) with respect to the resin solid content are mixed and stirred, and then diluted with propylene glycol monomethyl ether, Composition 1 having a resin solid content of 40 parts by weight was obtained.

(Manufacture of laminated body)
The obtained composition 1 was manufactured into a laminate 1 under the following conditions. Various tests were performed on the obtained laminate 1.

<Coating>
・Bar coater coating A polycarbonate plate (CarboGlass Polish Clear, made by Asahi Glass Co., Ltd., thickness 2 mm) is coated with a composition 1 prepared in Table 2-1 so that the coating film thickness after drying is about 10 to 20 μm. Then, it was applied and dried in a dryer at 80° C. for 10 minutes.

<Curing>
Ultraviolet irradiation uses a high pressure mercury lamp manufactured by GS-YUASA Co., Ltd., and the irradiation energy per pass is at a peak illuminance of 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 abrasion test]
The surface of the laminate was rubbed in a Taber abrasion test by a method based on ASTM D1044 (wear wheel: CS-10F, load: 500 g, rotation speed: 500), and the haze difference from the initial state, that is, haze. The value change ΔH (%) is measured. The smaller the difference, the higher the abrasion resistance, and ΔHaze≦4.0 was set as the acceptable value.

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

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

A: White turbidity did not occur.
◯: There was some cloudiness.
×: White turbidity was clearly observed. ・In a contact thermostat and humidity chamber, after standing still at 50° C. and 95% for 360 hours, each of the above samples was returned to room temperature,
A 100-square cross-cut adhesion test was carried out.
◎: 100 mass adhesion ○: 50-99 mass adhesion ×: 0-50 mass adhesion

(Cold and heat resistance test)
-After repeating the crack cycle, each of the above samples was returned to room temperature and visually checked for changes in the surface layer of the laminate, and then allowed to stand still at -30°C for 1 hour and then at 110°C for 1 hour using a cold heat tester. did. This was carried out for 100 cycles.
⊚: No cracks occurred ◯: Cracks were slightly observed ×: Cracks were clearly generated

-With the adhesion cold heat tester, it was allowed to stand at -30°C for 1 hour and then at 110°C for 1 hour. After repeating this 100 cycles, each above-mentioned sample was returned to room temperature, and 100 squares cross-cut adhesion test was implemented.
◎: 100 mass adhesion ○: 50-99 mass adhesion ×: 0-50 mass adhesion

(SUV accelerated weather resistance test)
Using Iwasaki Electric's Super Accelerated Weathering Tester Super UV Tester (SUV), 4 hours irradiation panel temperature 63°C humidity 90%) and 4 hours condensation (black panel temperature 30°C humidity 95%) (irradiation intensity 100mW The black panel temperature was 63° C., the humidity was 70%, and the darkness was 4 hours (black 12 hours was one cycle), and 60 cycles were evaluated.

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

<Examples 2 to 20>
Coating agents 2 to 12 were obtained in the same manner as in Example 1, except that the blending ratios were changed to those shown in Tables 1-1 and 1-2. For each of the obtained compositions, laminates 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): 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 blending ratio was changed to that shown in Table 2. For each composition obtained, 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 provide a cured product having excellent wear resistance, weather resistance, cold heat resistance, and wet heat resistance, it is possible to produce a laminate having excellent hard coat properties.

Claims (9)

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

   

   ...(1)
   (In the formula, each of X ₁ to X ₃ independently represents 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 represented by the formula (2 ) Is a 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 n1 is an integer of 1 to 3. ))
   

   

   ...(3)
   (In the formula, R ² represents an alkyl group having 1 to 15 carbon atoms, R ³ represents 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 is an integer of 1 to 3, and n3 is an integer of 1 to 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).)
2. The coating agent according to claim 1, wherein either Y ₁ 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 represents a bonding group having a urea or urethane bond, n3 represents a number of 1 to 3, l represents a number of 1 to 10, and m represents a number of 1 to 10.
3. Furthermore, the coating agent according to claim 1 or 2, wherein the silane condensate contains a structure (C) represented by the following formula (5).
   

   

   ...(5)
4. It 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) has at least a urethane or urea bond. A coating agent containing a condensate of a composition having one.
   

   

   ...(6)
   (In the formula, X ₄ to X ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or a group represented by the formula (7), and at least one of X ₄ to X ₆ is represented by the formula (7 ) Is a 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, wherein R ¹⁰ represents an organic group having 1 to 15 carbon atoms, and R 3 ¹¹ represents an organic group having 1 to 15 carbon atoms or a hydrogen atom, and n4 represents an integer of 1 to 3.
   

   

   ...(8)
   (In the formula, R ¹² and R ¹³ represent an alkyl group having 1 to 15 carbon atoms or a hydrogen atom, and R ¹⁴ represents a hydrogen atom or a methyl group,
   Y ₄ is a bonding group having at least one of an alkyl group having 1 to 10 carbon atoms, a urea bond and a urethane bond, n5 is an integer of 1 to 3, and n6 is an integer of 1 to 3. Show. )
5. The coating agent according to claim 4, wherein either Y ₃ or Y ₄ has a structure represented by the following formula (9).
   

   

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