JP2020172561A - Composition, cured film, and laminate - Google Patents

Abstract

To provide a composition that has excellent storage stability and is made into a cured film to have excellent anti-fogging properties and appearance, a cured film formed from the composition, and a laminate having the cured film.SOLUTION: A composition contains a copolymer and a specific alcohol, in which the copolymer contains specific four repeating units, and the content of the alcohol is 10 or more in mass ratio relative to the content of a specific one of the repeating units.SELECTED DRAWING: None

Description

The present invention relates to compositions, cured films, and laminates.

In vehicle lighting equipment such as headlamps of automobiles, high-humidity air enters the lighting chamber, the lens is cooled by outside air, rainfall, etc., and moisture condenses on the inner surface of the lens, which may cause fogging. As a result, the brightness of the vehicle light is reduced and the aesthetic appearance of the lens surface is impaired, which may cause discomfort to the user. In order to prevent such fogging of the inner surface of the lens, a method of applying an antifogging agent composition to the inner surface of the lens to form an antifogging coating film is known (for example, Patent Document 1).

JP-A-2017-8217

Under these circumstances, the present inventors have examined the composition of the example of Patent Document 1 (composition using propylene glycol monomethyl ether as a solvent), and as a result, the antifogging property and appearance of the obtained cured film are recently required. It became clear that it did not meet the required level. It was also found that the storage stability was insufficient.

Therefore, in view of the above circumstances, the present invention has a composition excellent in storage stability and excellent antifogging property and appearance when formed into a cured film, a cured film formed from the composition, and the cured film. It is an object of the present invention to provide a laminate provided with a film.

As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by using a copolymer containing four kinds of specific repeating units and blending a predetermined amount of a specific alcohol. It led to the invention.
That is, the present inventors have found that the above problems can be solved by the following configuration.

(1) A composition containing a copolymer and an alcohol.
The above copolymer
A repeating unit A selected from the group consisting of a repeating unit A1 represented by the formula (A1) described later and a repeating unit A2 represented by the formula (A2) described later.
The repeating unit B1 represented by the formula (B1) described later and
The repeating unit C1 represented by the formula (C1) described later and
It is a copolymer containing a repeating unit C2 represented by the formula (C2) described later.
The alcohol is represented by R-OH, where R is an unsubstituted alkyl group.
A composition in which the content of the alcohol is 10 or more by mass ratio with respect to the content of the repeating unit C1.
(2) In the above copolymer,
The content of the repeating unit A is 20 to 70% by mass.
The composition according to (1) above, wherein the content of the repeating unit B1 is 20 to 70% by mass.
(3) In the above copolymer,
The composition according to (1) or (2) above, wherein the ratio of the content of the repeating unit C2 to the content of the repeating unit C1 is 1 to 30 in terms of molar ratio.
(4) In the above copolymer,
The content of the repeating unit C1 is 0.5 to 10% by mass.
The composition according to any one of (1) to (3) above, wherein the content of the repeating unit C2 is 0.5 to 10% by mass.
(5) Further, it contains at least one specific ester monomer selected from the group consisting of a phosphate ester monomer and a fatty acid ester monomer.
The composition according to any one of (1) to (4) above, wherein the content of the specific ester monomer is 0.01 to 1 part by mass with respect to 100 parts by mass of the copolymer.
(6) A cured film formed from the composition according to any one of (1) to (5) above.
(7) A laminate comprising a resin substrate and the cured film according to (6) above.

As shown below, according to the present invention, a composition having excellent storage stability and excellent antifogging property and appearance when formed into a cured film, a cured film formed from the composition, and the cured film. A laminate provided with a film can be provided.

Hereinafter, the composition of the present invention, a cured film formed from the composition, and a laminate having the cured film will be described.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In addition, each component contained in the composition of the present invention may be used alone or in combination of two or more. Here, when two or more kinds of each component are used in combination, the content of the component means the total content unless otherwise specified.

[Composition]
The composition of the present invention is a composition containing a copolymer and an alcohol.
The above copolymer
A repeating unit A selected from the group consisting of a repeating unit A1 represented by the formula (A1) described later and a repeating unit A2 represented by the formula (A2) described later.
The repeating unit B1 represented by the formula (B1) described later and
The repeating unit C1 represented by the formula (C1) described later and
It is a copolymer (hereinafter, also referred to as "specific copolymer") containing a repeating unit C2 represented by the formula (C2) described later.
The alcohol is represented by R-OH, where R is an unsubstituted alkyl group.
A composition in which the content of the alcohol is 10 or more by mass ratio with respect to the content of the repeating unit C1.

Since the composition of the present invention has such a structure, it is considered that the above-mentioned effects can be obtained. The reason is not clear, but it is presumed to be as follows.
As described above, the composition of the present invention contains four specific repeating units (repeating unit A, repeating unit B1, repeating unit C1, repeating unit C2). When the composition of the present invention is heated, the alkoxysilyl groups in the repeating unit C1 react with each other, and the alkoxysilyl group in the repeating unit C1 reacts with the −OH group in the repeating unit C2 (crosslinking). It is considered that a cured film is formed.
Here, since the composition of the present invention contains a predetermined amount of alcohol with respect to the repeating unit C1, it is considered that the above reaction is unlikely to occur before heating and the storage stability is excellent. Then, when the alcohol is volatilized by heating, the equilibrium is deviated and the reaction occurs, and it is considered that a cured film is formed. In particular, since the alcohol does not have a substituent, it is considered that the contribution to the equilibrium reaction is high.

Hereinafter, each component contained in the composition of the present invention will be described.

[Specific copolymer]
As described above, the compositions of the present invention
A repeating unit A selected from the group consisting of a repeating unit A1 represented by the following formula (A1) and a repeating unit A2 represented by the following formula (A2), and a repeating unit A.
The repeating unit B1 represented by the following formula (B1) and
The repeating unit C1 represented by the following formula (C1) and
It contains a copolymer (specific copolymer) containing a repeating unit C2 represented by the following formula (C2).

In formulas (A1), (A2), (B1), (C1) and (C2), R represents a hydrogen atom or a methyl group.
In formula (A1), ^RA1 represents a hydrogen atom or a hydrocarbon group. The two ^RA1s may be the same or different.
In formula (A2), ^RA2 represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 or more.
In formula (B1), ^RB1 represents a hydrocarbon group.
In formula (C1), L represents a single bond or a divalent linking group. ^RC11 and ^RC12 each independently represent a hydrocarbon group. m represents an integer of 1 to 3. n represents an integer of 0 to 2. However, m + n = 3. When m is an integer of 2 or more, a plurality of ^RC11s existing may be the same or different. The two ^RC12s when n is 2 may be the same or different.
In the formula (C2), ^RC2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group.

The specific copolymer may be a random copolymer or a block copolymer.
The specific copolymer is excellent in curability and storage stability in the composition of the present invention, and when the composition of the present invention is formed into a cured film, it has antifogging property, adhesion, scratch resistance, and antifogging durability. Block copolymers are preferred because of their superior properties, water resistance and appearance. Hereinafter, "the composition of the present invention is superior in curability and storage stability, and when the composition of the present invention is formed into a cured film, antifogging property, adhesion, scratch resistance, antifogging durability, and water resistance "It is superior in character and appearance" is also referred to as "the effect of the present invention is more excellent".
The specific copolymer may contain a repeating unit other than the repeating unit described above.
Examples of the shape of the specific copolymer include a linear shape, a graft shape, a star shape, and the like, and among them, the linear shape is preferable because the effect of the present invention is more excellent.

<Repeating unit A>

The specific copolymer includes a repeating unit A selected from the group consisting of the repeating unit A1 represented by the following formula (A1) and the repeating unit A2 represented by the following formula (A2). The specific copolymer preferably contains the repeating unit A1 because the effects of the present invention and the like are more excellent.

In formula (A1), R represents a hydrogen atom or a methyl group. ^RA1 represents a hydrogen atom or a hydrocarbon group. The two ^RA1s may be the same or different.

As described above, in the formula (A1), ^RA1 represents a hydrogen atom or a hydrocarbon group.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these.
The aliphatic hydrocarbon group may be linear, branched or cyclic. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), and the like. Examples thereof include a linear or branched alkynyl group (particularly, having 2 to 30 carbon atoms).
Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xsilyl group and a naphthyl group.
The ^RA1 is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group, and even more preferably a linear alkyl group, for the reason that the effects of the present invention are more excellent. A linear alkyl group having 1 to 5 carbon atoms is particularly preferable.

In formula (A2), R represents a hydrogen atom or a methyl group. ^RA2 represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 or more.

As described above, in the formula (A2), ^RA2 represents a hydrogen atom or a hydrocarbon group.
Specific examples and preferred embodiments of the ^{R A2} is the same as ^{R A1} in the formula (A1).

As described above, in the formula (A2), p represents an integer of 1 or more.
The upper limit of p is not particularly limited, but is preferably 10 or less for the reason that the effect of the present invention is more excellent.

(Content)
In the specific copolymer, the content of the repeating unit A is preferably 20 to 70 mol%, more preferably 30 to 60 mol%, and more preferably 40 to 40 mol%, for the reason that the effect of the present invention is more excellent. It is more preferably 50 mol%.

In the specific copolymer, the content of the repeating unit A is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and 40 to 40 to 70% by mass, for the reason that the effect of the present invention is more excellent. It is more preferably 50% by mass.

<Repeating unit B1>
The specific copolymer contains a repeating unit B1 represented by the following formula (B1).

In formula (B1), R represents a hydrogen atom or a methyl group.
In formula (B1), ^RB1 represents a hydrocarbon group.

As described above, in formula (B1), ^RB1 represents a hydrocarbon group.
Specific examples and preferred embodiments of the hydrocarbon group are the same as R ^A1 in the formula (A1).

(Content)
In the specific copolymer, the content of the repeating unit B1 is preferably 20 to 70 mol%, more preferably 30 to 60 mol%, and more preferably 40 to 40 mol% because the effect of the present invention is more excellent. It is more preferably 50 mol%.

In the specific copolymer, the content of the repeating unit B1 is preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and 40 to 40 to 70% by mass, for the reason that the effect of the present invention is more excellent. It is more preferably 50% by mass.

<Repeating unit C1>
The specific copolymer contains a repeating unit C1 represented by the following formula (C1).

In formula (C1), L represents a single bond or a divalent linking group. ^RC11 and ^RC12 each independently represent a hydrocarbon group. m represents an integer of 1 to 3. n represents an integer of 0 to 2. However, m + n = 3. When m is an integer of 2 or more, a plurality of ^RC11s existing may be the same or different. The two ^RC12s when n is 2 may be the same or different.

As described above, in formula (C1), L represents a single bond or a divalent linking group.
Examples of the divalent linking group include a linear, branched or cyclic divalent aliphatic hydrocarbon group (for example, an alkylene group such as a methylene group, an ethylene group and a propylene group) and a divalent aromatic group. Hydrocarbon groups (eg, phenylene groups), -O-, -S-, -SO _2- , -NR _L- , -CO-, -NH-, -COO-, -CONR _L- , -O-CO- O-, -SO _3- , -NHCOO-, -SO ₂ NR _L- , -NH-CO-NH- or a group combining two or more of these (for example, alkyleneoxy group, alkyleneoxycarbonyl group, alkylenecarbonyloxy) (Group, etc.) and so on. Here, _RL represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
The above L is preferably an alkyleneoxycarbonyl group because the effect of the present invention is more excellent.

As described above, in the formula (C1), ^RC11 and ^RC12 each independently represent a hydrocarbon group.
Specific examples and preferred embodiments of the hydrocarbon group are the same as R ^A1 in the formula (A1).

As described above, in the formula (C1), m represents an integer of 1 to 3. n represents an integer of 0 to 2. However, m + n = 3.
The above m and n are preferably m = 3 and n = 0 for the reason that the effect of the present invention is more excellent.

(Content)
In the specific copolymer, the content of the repeating unit C1 is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, for the reason that the effect of the present invention is more excellent. It is preferably 0.5 to 5 mol%, more preferably 0.5 to 5 mol%.

In the specific copolymer, the content of the repeating unit C1 is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, for the reason that the effect of the present invention is more excellent. It is preferably 0.5 to 5% by mass, more preferably 0.5 to 5% by mass.

<Repeating unit C2>
The specific copolymer has a repeating unit C2 represented by the following formula (C2).

In formula (C2), R represents a hydrogen atom or a methyl group. ^RC2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group.

As described above, in the formula (C2), ^RC2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group.
Specific examples and preferred embodiments of the hydrocarbon group in the hydrocarbon group having the hydroxy group is the same as R ^A1 in the formula (A1).
Examples of the hydrocarbon group having a hydroxy group include a 2-hydroxyethyl group.

(Content)
In the specific copolymer, the content of the repeating unit C2 is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, for the reason that the effect of the present invention is more excellent. It is preferably 0.5 to 5 mol%, more preferably 0.5 to 5 mol%.

In the specific copolymer, the content of the repeating unit C2 is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, for the reason that the effect of the present invention is more excellent. It is preferably 0.5 to 5% by weight, and more preferably 0.5 to 5%.

<C1 + C2>
In the specific copolymer, the total content of the repeating unit C1 and the repeating unit C2 is preferably 0.1 to 20 mol%, preferably 0.2 to 10 mol%, for the reason that the effect of the present invention is more excellent. It is more preferably%, and even more preferably 0.3 to 5 mol%.

<C2 / C1>
In the specific copolymer, the ratio (molar ratio) of the content of the repeating unit C2 to the content of the repeating unit C1 (hereinafter, also referred to as “C2 / C1”) is 1 because the effect of the present invention is more excellent. It is preferably ~ 30, preferably 2-10.

<Specific block copolymer>
The specific copolymer is used because the effect of the present invention is more excellent.
A polymer block A having a repeating unit A selected from the group consisting of the repeating unit A1 and the repeating unit A2,
Including the polymer block B having the repeating unit B1 represented by the formula (B1),
At least one of the polymer block A and the polymer block B has a repeating unit C1 represented by the following formula (C1).
A block copolymer (hereinafter, also referred to as "specific block copolymer") in which at least one of the polymer block A and the polymer block B has a repeating unit C2 represented by the following formula (C2). It is preferable to have.

The specific block copolymer may be a diblock copolymer of one polymer block A and one polymer block B, or a multi-block copolymer in which at least one of each polymer block is present in a plurality. May be good. Further, the specific block copolymer may have a polymer block that does not correspond to either the polymer block A or the polymer block B.
The specific block copolymer is preferably a diblock copolymer of one polymer block A and one polymer block B because the effects of the present invention are more excellent.
Examples of the shape of the specific block copolymer include a linear shape, a graft shape, a star shape, and the like, and among them, the linear shape is preferable because the effect of the present invention is more excellent.

(Polymer block A)
The content of the repeating unit A in the polymer block A is preferably 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more, for the reason that the effect of the present invention is more excellent. Is more preferable. The upper limit of the total content of the repeating unit A in the polymer block A is not particularly limited and is 100 mol%.
The "content of repeating unit A in polymer block A" (mol%) is the ratio (mol%) of the total (number of moles) of repeating units A to all the repeating units (number of moles) of polymer block A. ) Means.

In the specific block copolymer, the content of the polymer block A is preferably 20 to 95 mol%, more preferably 30 to 90 mol%, for the reason that the effect of the present invention is more excellent. It is more preferably 40 to 80 mol%.
The "content of polymer block A" (mol%) is the ratio (mol%) of all repeating units (number of moles) of polymer block A to all repeating units (number of moles) of the specific block copolymer. Means.

In the specific block copolymer, the content of the polymer block A is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, for the reason that the effect of the present invention is more excellent. It is more preferably 40 to 80% by mass.

(Polymer block B)
The content of the repeating unit B1 in the polymer block B is preferably 50 mol% or more, more preferably 70 mol% or more, and 90 mol% or more, for the reason that the effect of the present invention is more excellent. Is more preferable. The upper limit of the content of the repeating unit B1 in the polymer block B is not particularly limited and is 100 mol%.
The "content of the repeating unit B1 in the polymer block B" (mol%) is the ratio (mol%) of the repeating unit B1 (number of moles) to the total number of repeating units (number of moles) of the polymer block B. means.

In the specific block copolymer, the content of the polymer block B is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, for the reason that the effect of the present invention is more excellent. It is more preferably 20 to 60 mol%.
The "content of polymer block B" (mol%) is the ratio (mol%) of all repeating units (number of moles) of polymer block B to all repeating units (number of moles) of the specific block copolymer. Means.

In the specific block copolymer, the content of the polymer block B is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, for the reason that the effect of the present invention is more excellent. It is more preferably 20 to 60% by mass.

(Polymer block A / Polymer block B)
In the specific block copolymer, the ratio of the content of the polymer block A to the content of the polymer block B (polymer block A / polymer block B) is a molar ratio because the effect of the present invention is more excellent. It is preferably 0.25 to 19, more preferably 0.42 to 9.0, and even more preferably 0.67 to 4.0.

(Polymer block A + Polymer block B)
In the specific block copolymer, the total content of the polymer block A and the polymer block B is preferably 50 mol% or more, preferably 70 mol% or more, for the reason that the effect of the present invention is more excellent. More preferably, it is more preferably 90 mol% or more. In the specific block copolymer, the upper limit of the total content of the polymer block A and the polymer block B is not particularly limited and is 100 mol%.
In addition, "total content of polymer block A and polymer block B" (mol%) means all repeating units of polymer block A and polymer block with respect to all repeating units (number of moles) of block copolymer. It means the ratio (mol%) of the total (number of moles) of all repeating units of B.

Further, in the specific block copolymer, the total content of the polymer block A and the polymer block B is preferably 50% by mass or more, preferably 70% by mass or more, for the reason that the effect of the present invention is more excellent. Is more preferable, and 90% by mass or more is further preferable. In the specific block copolymer, the upper limit of the total content of the polymer block A and the polymer block B is not particularly limited and is 100% by mass.

(Repeating unit C1)
As described above, in the specific block copolymer, at least one of the polymer block A and the polymer block B has the repeating unit C1.
It is preferable that at least the polymer block B has the repeating unit C1 for the reason that the effect of the present invention is more excellent, and it is more preferable that both the polymer block A and the polymer block B have the repeating unit C1.
The content of the repeating unit C1 in the polymer block A is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, for the reason that the effect of the present invention is more excellent. It is preferably 0.5 to 5 mol%, more preferably 0.5 to 5 mol%.
The content of the repeating unit C1 in the polymer block B is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, for the reason that the effect of the present invention is more excellent. It is preferably 0.5 to 5 mol%, more preferably 0.5 to 5 mol%.
The "content of repeating unit C1 in polymer block A" (mol%) is the ratio (mol%) of repeating unit C1 (number of moles) to all repeating units (number of moles) of polymer block A. The "content of the repeating unit C1 in the polymer block B" means the ratio (mol%) of the repeating unit C1 (number of moles) to the total number of repeating units (number of moles) of the polymer block B.

(Repeating unit C2)
The content of the repeating unit C2 in the polymer block A is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, for the reason that the effect of the present invention is more excellent. It is preferably 0.5 to 5 mol%, more preferably 0.5 to 5 mol%.
The content of the repeating unit C2 in the polymer block B is preferably 0.1 to 20 mol%, more preferably 0.2 to 10 mol%, for the reason that the effect of the present invention is more excellent. It is preferably 0.5 to 5 mol%, more preferably 0.5 to 5 mol%.
The "content of repeating unit C2 in polymer block A" (mol%) is the ratio (mol%) of repeating unit C2 (number of moles) to all repeating units (number of moles) of polymer block A. The "content of the repeating unit C2 in the polymer block B" means the ratio (mol%) of the repeating unit C2 (number of moles) to the total number of repeating units (number of moles) of the polymer block B.

<Molecular weight>

(Number average molecular weight)
The number average molecular weight (Mn) of the specific copolymer is not particularly limited, but is preferably 1,000 to 1,000,000, preferably 10,000 to 100,000, for the reason that the effects of the present invention are more excellent. Is more preferable, and 20,000 to 80,000 is even more preferable.

(Weight average molecular weight)
The weight average molecular weight (Mw) of the specific copolymer is not particularly limited, but is preferably 1,000 to 1,000,000, preferably 10,000 to 100,000, for the reason that the effects of the present invention are more excellent. Is more preferable, and 20,000 to 80,000 is even more preferable.

(Molecular weight distribution)
The molecular weight distribution (Mw / Mn) of the specific copolymer is not particularly limited, but is preferably 10 or less, and more preferably 5 or less, for the reason that the effects of the present invention are more excellent. The lower limit of the molecular weight distribution is not particularly limited, but is usually 1.0 or more.

The Mn and Mw are standard polystyrene-equivalent values obtained by gel permeation chromatography (GPC) measurement under the following conditions.
・ Solvent: Tetrahydrofuran ・ Detector: RI detector

<Manufacturing method>
The method for producing the specific copolymer is not particularly limited, and a conventionally known method can be used.

When the specific copolymer is a specific block copolymer, a method using a living radical polymerization method is preferable, and a method using a RAFT method (reversible addition cleavage chain transfer polymerization method) (particularly, a trithiocarbonate compound) is used. The method used as a chain transfer agent) is more preferable.
More specifically, for example, by the living radical polymerization method, a monomer that becomes the repeating unit B1 (for example, methyl methacrylate), a monomer that becomes the repeating unit C1 (for example, 3-methacryloxypropyltrimethoxysilane), and the repeating unit C2. (For example, 2-hydroxyethyl methacrylate) is polymerized to produce the polymer block B, and then the monomer (for example, N, N-dimethylacrylamide) to be the repeating unit A1 and the repeating unit C1 are formed. A polymer block A is produced by polymerizing a monomer (for example, 3-methacryloxypropyltrimethoxysilane) and a monomer (for example, 2-hydroxyethyl methacrylate) to be a repeating unit C2, and the polymer block A is overlapped with the polymer block A. Examples thereof include a method of producing a block copolymer containing the coalesced block B (in this case, both the polymer block A and the polymer block B have the repeating unit C1).

<Content>
In the composition of the present invention, the content of the specific copolymer is preferably 1 to 50% by mass, preferably 10 to 40% by mass, based on the entire composition, for the reason that the effect of the present invention is more excellent. Is more preferable, and 20 to 30% by mass is further preferable.

[Specific alcohol]
As described above, the composition of the present invention contains an alcohol represented by R-OH (hereinafter, also referred to as "specific alcohol"). Here, R is an unsubstituted alkyl group.
The carbon number of the unsubstituted alkyl group is preferably 1 to 10 and more preferably 2 to 5 for the reason that the effect of the present invention is more excellent.
The unsubstituted alkyl group may be linear, branched or cyclic, but is preferably branched for the reason that the effect of the present invention is more excellent.

<Content>
In the composition of the present invention, the content of the specific alcohol is preferably 10 to 99% by mass, preferably 50 to 90% by mass, based on the whole composition, for the reason that the effect of the present invention is more excellent. More preferably, it is more preferably 70 to 80% by mass.

[Specific alcohol / C1]
In the composition of the present invention, the content of the above-mentioned specific alcohol is 10 or more by mass ratio with respect to the content of the repeating unit C1 of the above-mentioned specific copolymer.
Hereinafter, the content (mass ratio) of the specific alcohol with respect to the content of the repeating unit C1 is also referred to as "specific alcohol / C1".
The specific alcohol / C1 is preferably 20 or more, more preferably 50 or more, still more preferably 100 or more, for the reason that the effect of the present invention is more excellent.
The upper limit of the specific alcohol / C1 is not particularly limited, but it is preferably 1000 or less, more preferably 500 or less, still more preferably 200 or less, for the reason that the effect of the present invention is more excellent.

The specific alcohol / C1 is calculated as follows in the case of Example 1-1 described later, for example.
In Example 1-1, the content of the specific alcohol is 300 parts by mass with respect to 100 parts by mass of the specific copolymer. The content of the repeating unit C1 in the specific copolymer is 2.6% by mass. Therefore, the specific alcohol / C1 is 115 (= 300 ÷ (100 × 0.026)).

[Arbitrary component]
The composition of the present invention may contain components other than those described above.
Examples of such a component include polymers other than the above-mentioned specific copolymers, monomers, surfactants, leveling agents, solvents other than the above-mentioned specific alcohols, and the like.

<Specific ester monomer>
The composition of the present invention preferably further contains at least one specific ester monomer selected from the group consisting of a phosphate ester monomer and a fatty acid ester monomer, for the reason that the effects of the present invention are more excellent.

The specific ester monomer is preferably a phosphoric acid ester monomer because the effect of the present invention is more excellent.
The phosphoric acid ester monomer preferably has a (meth) acryloyloxy group, and more preferably an ester of phosphoric acid and a (meth) acrylate having a hydroxy group, for the reason that the effects of the present invention are more excellent.

In the composition of the present invention, the content of the specific ester monomer is 0.01 to 10 parts by mass with respect to 100 parts by mass of the block copolymer described above for the reason that the effect of the present invention is more excellent. It is preferably 0.1 to 1.0 parts by mass, more preferably 0.1 to 1.0 parts by mass.

<Solvents other than specific alcohols>
When the composition of the present invention contains a solvent other than the above-mentioned specific alcohol, the total content of the specific alcohol and the solvent other than the specific alcohol is based on the whole composition because the effect of the present invention is more excellent. It is preferably 10 to 99% by mass, and more preferably 50 to 90% by mass.

[Use]
The composition of the present invention is useful, for example, as an anti-fog coating agent (coating agent for preventing fogging).

[Cured film]
The cured film of the present invention is a cured film formed from the composition of the present invention described above.
The method for producing the cured film of the present invention is not particularly limited, but for example, the composition of the present invention described above is applied onto a substrate (preferably a resin substrate, more preferably a (meth) acrylate resin substrate) and heated (preferably). Is 50 to 200 ° C.).
By heating, the alkoxysilyl groups in the repeating unit C1 react with each other, and the alkoxysilyl groups in the repeating unit C1 react with (crosslink) the −OH groups in the repeating unit C2 to form a cured film. Is formed.
The cured film of the present invention is useful as, for example, an anti-fog film (a film for preventing fogging).

[Laminate]
The laminate of the present invention is a laminate having the above-mentioned cured film. Among them, a laminate having a resin substrate (preferably a (meth) acrylate resin substrate) and the above-mentioned cured film is preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[Example 1-1]
Isopropanol (150 parts by mass) (hereinafter, also referred to as "alcohol A") was charged into a reactor equipped with a stirrer, a thermometer, a cooling tube, a nitrogen gas introduction tube, and a dropping device, and the temperature was raised to 70 ° C. while stirring. .. There, 47.0 parts by mass of N, N-dimethylacrylamide, 47.7 parts by mass of methyl methacrylate, 2.7 parts by mass of 2-hydroxyethyl methacrylate, 3-methacryloxypropyltrimethoxysilane (Shinetsu Chemical Industry Co., Ltd.) ) KBM-503) 2.6 parts by mass, 3.0 parts by mass of azobisisobutyronitrile, 150 parts by mass of isopropyl alcohol (hereinafter, also referred to as "alcohol B") was added dropwise over 4 hours. .. After completion of the dropping, the reaction was carried out at the same temperature for 12 hours to obtain a random copolymer in a yield of 100%.
In this way, the composition of Example 1-1 containing a random copolymer (100 parts by mass) and a specific alcohol (isopropanol) (300 parts by mass) was obtained.
The random copolymers in the composition of Example 1-1 were a repeating unit derived from N, N-dimethylacrylamide (corresponding to the repeating unit A1 described above) (48.5 mol%) and methyl methacrylate (repeating described above). Unit B1 (corresponding to unit B1) (48.5 mol%), repeating unit derived from 3-methacryloxypropyltrimethoxysilane (corresponding to repeating unit C1 described above) (1.0 mol%) and 2-hydroxyethyl methacrylate (corresponding to unit B1) (1.0 mol%). It is a random copolymer (linear) composed of the above-mentioned repeating unit C2) (2.0 mol%). The obtained random copolymer corresponds to the above-mentioned specific copolymer.

[Example 1-2]
As alcohol A, a specific alcohol (isopropanol) (15 parts by mass) and a solvent other than the specific alcohol (propylene glycol monomethyl ether (methoxyisopropanol)) (135 parts by mass) are used (the total of alcohol A is 150 parts by mass), and alcohol B. Examples except that a specific alcohol (isopropanol) (15 parts by mass) and a solvent other than the specific alcohol (propylene glycol monomethyl ether (methoxyisopropanol)) (135 parts by mass) were used (the total of alcohol B was 150 parts by mass). The composition of Example 1-2 was obtained according to the same procedure as 1-1.
The composition of Example 1-2 is other than a random copolymer (same as the random copolymer in Example 1-1) (100 parts by mass), a specific alcohol (isopropanol) (30 parts by mass), and a specific alcohol. It is a composition containing a solvent (propylene glycol monomethyl ether (methoxyisopropanol)) (270 parts by mass).

[Example 1-3]
The specific ester monomer (phosphate ester monomer) (PPME manufactured by Toho Chemical Industry Co., Ltd.) (0.25 parts by mass) was mixed with the composition of Example 1-1 to obtain the composition of Example 1-3. ..
The compositions of Examples 1-3 consist of a random copolymer (same as the random copolymer in Example 1-1) (100 parts by mass), a specific alcohol (isopropanol) (300 parts by mass), and a specific ester monomer (300 parts by mass). It is a composition containing a phosphoric acid ester monomer) (PPME manufactured by Toho Kagaku Kogyo Co., Ltd.) (0.25 parts by mass).

[Comparative Example 1-1]
As alcohol A, a specific alcohol (isopropanol) (10 parts by mass) and a solvent other than the specific alcohol (propylene glycol monomethyl ether (methoxyisopropanol)) (140 parts by mass) are used (the total of alcohol A is 150 parts by mass), and alcohol B. Examples except that a specific alcohol (isopropanol) (10 parts by mass) and a solvent other than the specific alcohol (propylene glycol monomethyl ether (methoxyisopropanol)) (140 parts by mass) were used (the total of alcohol B was 150 parts by mass). The composition of Comparative Example 1-1 was obtained according to the same procedure as 1-1.
The composition of Comparative Example 1-1 is other than a random copolymer (the same as the random copolymer in Example 1-1) (100 parts by mass), a specific alcohol (isopropanol) (20 parts by mass), and a specific alcohol. It is a composition containing a solvent (propylene glycol monomethyl ether (methoxyisopropanol)) (280 parts by mass).

Table 1 shows the content (molar%, mass%) of each repeating unit derived from each monomer in the random copolymer for each composition. In addition, Table 1 shows the content (parts by mass) of each component for each composition. The mass part of each component is a mass part as a solid content.

[Example 2-1]
The composition of Example 2-1 was produced as follows.

<Synthesis of block copolymer>
Methyl methacrylate (manufactured by Tokyo Chemical Industry: 16 mL), 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry: 0.4 mL), 3-methacryloxypropyltrimethoxysilane (manufactured by Shinetsu Silicone: 0.4 mL), azobisiso Butyronitrile (manufactured by Tokyo Chemical Industry: 10 mg), 4-cyano-4-(((dodecylthio) carbotioil) thio) pentanoic acid (manufactured by Boron Molecular: 0.12 g) and N, N-dimethylformamide (manufactured by Kanto Chemical Co., Inc .:) 50 mL) was mixed, heated to 70 ° C., and stirred. After 20 hours, N, N-dimethylacrylamide (manufactured by Tokyo Chemical Industry: 15.4 mL), 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry: 0.4 mL) and 3-methacryloxypropyltrimethoxysilane (manufactured by Shinetsu Silicone) : 0.4 mL) was added, heated to 70 ° C., and stirred. After 40 hours, the mixture was cooled to room temperature to terminate the polymerization. The obtained polymer solution was taken out and concentrated under reduced pressure. As a result, a block copolymer (31.0 g, Mn = 40,000, Mw = 48,000, PDI = 1.2) was obtained in a yield of 99%.
The obtained block copolymer is a repeating unit derived from N, N-dimethylacrylamide (corresponding to the repeating unit A1 described above) (97 mol%) and a repeating unit derived from 3-methacryloxypropyltrimethoxysilane (described above). Polymer block A (corresponding to the above-mentioned polymer block A) composed of the repeated unit C1 (corresponding to the above-mentioned repeating unit C1) (1 mol%) and 2-hydroxyethyl methacrylate (corresponding to the above-mentioned repeating unit C2) (2 mol%). , Methyl methacrylate (corresponding to the above-mentioned repeating unit B1) (97 mol%), a repeating unit derived from 3-methacryloxypropyltrimethoxysilane (corresponding to the above-mentioned repeating unit C1) (1 mol%) and methacrylic acid. It is a block copolymer (linear) containing a polymer block B (corresponding to the above-mentioned polymer block B) composed of 2-hydroxyethyl (corresponding to the above-mentioned repeating unit C2) (2 mol%). The content of the polymer block A in the block copolymer is 50 mol%, and the content of the polymer block B in the block copolymer is 50 mol%. The obtained block copolymer corresponds to the above-mentioned specific block copolymer.

<Preparation of composition>
The obtained block copolymer (100 parts by mass) and a specific alcohol (isopropanol) (300 parts by mass) were mixed to prepare the composition of Example 2-1. The mass part of each component (other than the solvent) is the mass part as a solid content.

[Examples 2-2-2-3 and Comparative Example 2-1]
The mass part of the specific alcohol is changed as shown in Table 2, and the solvent other than the specific alcohol is mixed for the example described in the column of the solvent other than the specific alcohol, and the example described in the column of the specific ester monomer is mixed. Each composition was prepared according to the same procedure as in Example 2-1 except that the specific ester monomer was further mixed.

In addition, Table 2 shows each repeating unit (mass%) derived from each monomer together with each repeating unit (mol%) derived from each monomer. In addition, Table 2 shows the content (mass%) of each block together with the content (mol%) of each block.
Further, in Table 2, the mass part of each component in the column of composition is the mass part as a solid content.

[Evaluation]
The following evaluations were carried out for each of the obtained compositions.

<Anti-fog>
Each of the obtained compositions is coated on a methyl methacrylate resin substrate by a spray coating method so that the film thickness of the coating film (cured film) after curing is 3 to 5 μm, and dried at 30 ° C. for 1 minute. After that, it was heated at 100 ° C. until it was sufficiently cured. In this way, a cured film was obtained.
The obtained cured film was placed at a height of 5 cm from the water surface of the hot water bath kept at 40 ° C., steam from the hot water bath was continuously applied to the cured film, and 30 seconds after the start of applying steam. The presence or absence of cloudiness was visually confirmed.
Based on the result of the presence or absence of fogging, the fogging property was evaluated in the following three stages. The results are shown in Tables 1-2. Practically, it is preferably 2 or more.
3: It was not cloudy at all.
2: It was slightly cloudy.
1: Clear cloudiness was observed.

<Adhesion>
As described above, a cured film was obtained. The obtained cured film was evaluated for adhesion in the following eight stages by JIS K 5600-5-6 (cross-cut method). The results are shown in Tables 1-2. Practically, it is preferably 2 or more.
8: The number of peels in 100 squares is less than 5 7: The number of peels in 100 squares is 5 or more and less than 10 6: The number of peels in 100 squares is 10 or more and less than 15 5: 100 peels in squares The number of occurrences is 15 or more and less than 20 4: The number of peeling in 100 squares is 20 or more and less than 25 3: The number of peeling in 100 squares is 25 or more and less than 30 2: The number of peeling in 100 squares is 30 Less than 35 1: The number of peels in 100 squares is 35 or more

<Scratch resistance>
As described above, a cured film was obtained. The obtained cured film was examined for pencil hardness (the hardness of the hardest pencil that did not cause scratches) by a pencil hardness test, and the scratch resistance was evaluated in the following eight stages. The results are shown in Tables 1-2. Practically, it is preferably 2 or more.
8: Pencil hardness is 4H or more 7: Pencil hardness is 3H
6: Pencil hardness is 2H
5: Pencil hardness is H
4: Pencil hardness is F
3: Pencil hardness is HB
2: Pencil hardness is B
1: Pencil hardness is 2B or less

<Anti-fog durability>
As described above, a cured film was obtained. The obtained cured film was exposed to steam from a humidifier at room temperature for 10 seconds, separated from the steam once, allowed to stand for about 1 minute, and then steamed from a humidifier for 10 seconds to be separated from the steam once. This was repeated 10 times, and the one without cloudiness was designated as 2, and the one with cloudiness was designated as 1. The results are shown in Table 1.

<Curable>
Each of the obtained compositions is coated on a methyl methacrylate resin substrate by a spray coating method so that the film thickness of the coating film (cured film) after curing is 3 to 5 μm, and dried at 30 ° C. for 1 minute. After that, it was heated at 100 ° C. Then, the curability was evaluated in the following four stages. The results are shown in Tables 1-2.
Cures within 4: 5 minutes.
It cures in more than 3: 5 minutes and less than 10 minutes.
It cures in more than 2:10 minutes and less than 20 minutes.
1: It takes 20 minutes or more to cure.

<Water resistance>
As described above, a cured film was obtained. The obtained cured film was immersed in warm water at 40 ° C. for 240 hours, and after immersion, the laminate was pulled up from the warm water, and the appearance of the cured film was visually observed. Then, the water resistance was evaluated in the following seven stages. The results are shown in Tables 1-2.
7: It was exactly the same as the cured film before immersion, and no change was observed.
6: Slight turbidity was observed, but the area was less than 5%.
5: The area where turbidity was observed was 5% or more and less than 10%.
4: The area where turbidity was observed was 10% or more and less than 15%.
3: The area where turbidity was observed was 15% or more and less than 20%.
2: The area where turbidity was observed was 20% or more and less than 25%.
1: The area where turbidity was observed was 25% or more.

<Appearance>
As described above, a cured film was obtained. The obtained cured film was visually observed. Then, the appearance was evaluated in the following three stages. The results are shown in Tables 1-2. Practically, it is preferably 2 or more.
3: Overall smooth.
2: A wavy shape and a citron skin shape were partially observed.
1: Wavy shape and yuzu skin shape were observed as a whole.

<Storage stability>
Each of the obtained compositions was placed in an oven or refrigerator (freezer) at 50 ° C., room temperature, 5 ° C., and −10 ° C., and allowed to stand for 4 weeks, after which the liquid properties and coating film performance were confirmed. Then, those in which no change was confirmed as compared with those before standing still were set as 2, and those in which even one item was confirmed as compared with before standing was set as 1. The results are shown in Tables 1-2. Practically, it is preferably 2.

In Tables 1 and 2, the specific ester monomers, specific alcohols, and solvents other than the specific alcohols are as follows.
-Specific ester monomer: Phosphate ester monomer (PPME manufactured by Toho Chemical Industry Co., Ltd.) (structure below)

-Specific alcohol: isopropanol-Solvents other than specific alcohol: Propylene glycol monomethyl ether (methoxyisopropanol)

In Tables 1 and 2, "specific alcohol / C1" means the above-mentioned specific alcohol / C1.

As can be seen from Table 1, Examples 1-1 to 1-3 in which the specific alcohol / C1 is 10 or more are excellent in anti-fog as compared with Comparative Example 1-1 in which the specific alcohol / C1 is less than 10. It showed sex, appearance and storage stability. Among them, Examples 1-1 and 1-3 in which the specific alcohol / C1 was 100 or more showed more excellent antifogging property, adhesion, scratch resistance, curability, water resistance and appearance. Among them, Examples 1-3 containing the specific ester monomer showed further excellent adhesion, scratch resistance, curability and water resistance.

Further, as can be seen from Table 2, Examples 2-1 to 2-3 having a specific alcohol / C1 of 10 or more were superior to Comparative Example 2-1 having a specific alcohol / C1 of less than 10. It showed anti-fog property, appearance and storage stability. Among them, Examples 2-1 and 2-3 in which the specific alcohol / C1 was 100 or more showed more excellent antifogging property, adhesion, scratch resistance, curability, water resistance and appearance. Among them, Examples 2-3 containing the specific ester monomer showed further excellent adhesion, scratch resistance, curability and water resistance.

Claims (7)

A composition containing a copolymer and an alcohol.
The copolymer
A repeating unit A selected from the group consisting of a repeating unit A1 represented by the following formula (A1) and a repeating unit A2 represented by the following formula (A2), and a repeating unit A.
The repeating unit B1 represented by the following formula (B1) and
The repeating unit C1 represented by the following formula (C1) and
It is a copolymer containing the repeating unit C2 represented by the following formula (C2).
The alcohol is represented by R-OH, where R is an unsubstituted alkyl group.
A composition in which the content of the alcohol is 10 or more by mass ratio with respect to the content of the repeating unit C1.




In formulas (A1), (A2), (B1), (C1) and (C2), R represents a hydrogen atom or a methyl group.
In formula (A1), ^RA1 represents a hydrogen atom or a hydrocarbon group. The two ^RA1s may be the same or different.
In formula (A2), ^RA2 represents a hydrogen atom or a hydrocarbon group. p represents an integer of 1 or more.
In formula (B1), ^RB1 represents a hydrocarbon group.
In formula (C1), L represents a single bond or a divalent linking group. ^RC11 and ^RC12 each independently represent a hydrocarbon group. m represents an integer of 1 to 3. n represents an integer of 0 to 2. However, m + n = 3. When m is an integer of 2 or more, a plurality of ^RC11s existing may be the same or different. The two ^RC12s when n is 2 may be the same or different.
In the formula (C2), ^RC2 represents a hydrogen atom or a hydrocarbon group having a hydroxy group. In the copolymer
The content of the repeating unit A is 20 to 70% by mass, and the content is 20 to 70% by mass.
The composition according to claim 1, wherein the content of the repeating unit B1 is 20 to 70% by mass. In the copolymer
The composition according to claim 1 or 2, wherein the ratio of the content of the repeating unit C2 to the content of the repeating unit C1 is 1 to 30 in terms of molar ratio. In the copolymer
The content of the repeating unit C1 is 0.5 to 10% by mass.
The composition according to any one of claims 1 to 3, wherein the content of the repeating unit C2 is 0.5 to 10% by mass. Further, it contains at least one specific ester monomer selected from the group consisting of a phosphate ester monomer and a fatty acid ester monomer.
The composition according to any one of claims 1 to 4, wherein the content of the specific ester monomer is 0.01 to 1 part by mass with respect to 100 parts by mass of the copolymer. A cured film formed from the composition according to any one of claims 1 to 5. A laminate comprising a resin substrate and the cured film according to claim 6.