JP6075443B2 - Active energy ray-curable coating composition - Google Patents

Description

The present invention relates to an active energy ray-curable coating composition, and belongs to the technical field of an active energy ray-curable composition and a coating material.

In recent years, glass has been used for displays such as touch panels and smartphones, which are rapidly spreading, but studies are underway to replace them with plastics for the purpose of reducing weight and preventing glass scattering when broken. .
In general, a plastic substrate is lightweight and excellent in impact resistance, easy moldability, and the like. However, since the surface is easily damaged and has low hardness, there is a drawback that the appearance is remarkably impaired when used as it is. For this reason, the surface of a plastic substrate is often painted with a coating composition and subjected to a so-called hard coat treatment to impart abrasion resistance, scratch resistance, and the like.

The conventional coating composition uses a coating composition in which a resin is dissolved in a solvent, and is applied to a substrate and then dried to form a resin film. For the purpose of improving productivity, etc. Further, photocurable compositions and thermosetting compositions have been studied.
Here, as a hard coating agent for a plastic substrate, an ultraviolet curable acrylic hard coating agent, a thermosetting silicone hard coating agent, and the like have been proposed.
Thermosetting silicone hard coat agent is excellent in abrasion resistance and scratch resistance, but the curing time is long and the productivity is inferior, and the substrate may be deformed because a high temperature is required at the time of curing. There are problems such as. On the other hand, the ultraviolet curable acrylic hard coat agent is generally inferior in abrasion resistance and scratch resistance, but has a short curing time and excellent productivity.

As described above, the ultraviolet curable acrylic hard coating agent is superior to the thermosetting composition in terms of productivity and energy saving. Investigations have been made to improve wear and scratch resistance.
For example, a method of blending a composition with colloidal silica or a silane compound having a (meth) acryloyloxy group is known.
Specifically, colloidal silica, an ultraviolet curable coating composition containing an alkoxysilane and acrylate having a (meth) acryloyloxy group (Patent Document 1), an isocyanate-containing alkoxysilane, a hydroxyl group and three or more acryloyl groups in the molecule There is known an ultraviolet curable coating composition (Patent Document 2) containing a reaction product with a polyfunctional acrylate having a polyfunctional acrylate, a polyfunctional acrylate having three or more acryloyl groups, and colloidal silica.
However, these coating compositions are excellent in abrasion resistance and scratch resistance of the cured film as compared with conventional UV curable coating compositions, but cannot satisfy both abrasion resistance and scratch resistance at the same time. Or did not have satisfactory performance in practice. In addition, the adhesion may be insufficient depending on the substrate used.

  On the other hand, the applicant has proposed a photocurable coating composition containing a specific organosilicon compound as a hard coat agent excellent in abrasion resistance, scratch resistance, adhesion to a substrate, and the like. (Patent Document 3).

Special Publication No. 57-500904 Japanese Patent Publication No. 5-287215 JP 2011-88996 A

However, the photocurable coating composition described in Patent Document 3 requires an organic solvent in order to adjust the viscosity of the composition and impart coating suitability. For this reason, for example, when thick film coating is performed, it may take time to evaporate the solvent, and there is room for improvement.
Generally, when the viscosity of a composition is adjusted by adding a reactive monomer or the like in place of an organic solvent, the hardness and scratch resistance of the cured product are reduced, and the resulting cured film is sufficient as a hard coat. I was not satisfied. Therefore, there has been a demand for a coating composition that is solvent-free, satisfies hardness and scratch resistance, and can be cured by active energy rays such as electron beams and ultraviolet rays.

  In general, by adding an unsaturated compound having a long chain segment in the molecule to the curable composition, the Tg of the cured product is reduced and the impact resistance is improved. However, such a cured film has a tendency that the hardness and the scratch resistance are lowered because the crosslinking density is lowered. Therefore, there has been a demand for a curable composition that can provide a cured film that satisfies hardness and scratch resistance and also has excellent impact resistance.

  The present invention is an active energy ray-curable coating composition that does not contain an organic solvent, the viscosity of which is sufficiently reduced to allow coating, and the cured film when applied to a substrate such as plastic. It is an object to provide an active energy ray-curable coating composition exhibiting sufficient hardness and scratch resistance.

In addition, the present invention is sufficiently reduced in viscosity to enable coating, and when applied to a substrate such as plastic, the cured film exhibits sufficient hardness and scratch resistance, and has an impact resistance. It is an object of the present invention to provide an active energy ray-curable coating composition having excellent properties.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a composition containing a compound having a nitrogen atom and a radically polymerizable unsaturated group, so that the composition can be obtained without using an organic solvent. It was found that the product can be adjusted to a viscosity that can be sufficiently applied, and a cured product having excellent hardness and scratch resistance can be obtained. In addition, the present inventors have obtained a cured film having high hardness and excellent scratch resistance and impact resistance by using a composition containing a compound having an isocyanuric ring and a radically polymerizable unsaturated group. As a result, the present invention has been completed.

（一般式（１）において、Ｒ¹は炭素数１〜６のアルキル基、炭素数７〜１０のアラルキル基又は炭素数６〜１０のアリール基を有する有機基であり、Ｒ²は炭素数１〜６の２価の飽和炭化水素基であり、Ｒ³は水素原子又はメチル基であり、Ｘは加水分解性基であり、複数のＸは互いに同一であっても異なっていても良く、ｎは０又は１である。）
ＳｉＹ₄ ・・・（２）
（一般式（２）において、Ｙはシロキサン結合生成基であり、複数のＹは互いに同一であっても異なっていても良い。）
（Ｂ）３価以上の脂肪族多価アルコールから誘導される（メタ）アクリレートであって、（メタ）アクリロイル基を２個以上有し、水酸基を１個以上有する（メタ）アクリレートと、ポリイソシアネートとの付加反応で得られるウレタンアダクト化合物（ｂ１）、及び、３価以上の脂肪族多価アルコールから誘導される（メタ）アクリレートであって、（メタ）アクリロイル基を３個以上有し、水酸基を有さない（メタ）アクリレート（ｂ２）から構成される（メタ）アクリレート混合物、
並びに、
（Ｃ）分子内に窒素原子を有するラジカル重合性不飽和化合物であって、上記成分（Ａ）及び上記成分（Ｂ）以外の化合物、を含有し、
上記成分（Ａ）、上記成分（Ｂ）及び上記成分（Ｃ）の含有量は、これらの合計を１００重量部としたときに、上記成分（Ａ）が５〜５０重量部、上記成分（Ｂ）が３０〜９０重量部、上記成分（Ｃ）が５〜３５重量部である活性エネルギー線硬化型塗料組成物。
〔２〕上記化合物（ａ１）は、一般式（１）におけるＸがアルコキシ基であり且つｎが０である化合物であり、
上記化合物（ａ２）は、一般式（２）におけるＹがアルコキシ基である上記〔１〕に記載の活性エネルギー線硬化型塗料組成物。
〔３〕上記成分（Ｃ）が、モルホリニル基含有単量体、アミド基含有単量体、及び、ラクタム化合物から選ばれた少なくとも１種の化合物（Ｃ１）を含む上記〔１〕又は〔２〕に記載の活性エネルギー線硬化型塗料組成物。
〔４〕上記化合物（Ｃ１）が、アクリロイルモルホリン、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド及びＮ−ビニル−ε−カプロラクタムから選ばれた少なくとも１種である上記〔３〕に記載の活性エネルギー線硬化型塗料組成物。
〔５〕上記成分（Ｃ）が、イソシアヌル環を有する化合物（Ｃ２）を含み、該化合物（Ｃ２）の含有量が５〜３０重量部である上記〔１〕〜〔４〕のいずれかに記載の活性エネルギー線硬化型塗料組成物。
〔６〕上記化合物（Ｃ２）が、アルキレンオキシド又はカプロラクトンにより変性されたラジカル重合性不飽和化合物である上記〔５〕に記載の活性エネルギー線硬化型塗料組成物。
〔７〕上記成分（Ｃ）の含有量が、上記成分（Ａ）、上記成分（Ｂ）及び上記成分（Ｃ）の合計を１００重量部としたときに、１０〜３５重量部であり、上記成分（Ｃ）が、モルホリニル基含有単量体、アミド基含有単量体、及び、ラクタム化合物から選ばれた少なくとも１種の化合物（Ｃ１）と、イソシアヌル環を有する化合物（Ｃ２）とからなり、両者の合計を１０〜３５重量部とした場合に、上記化合物（Ｃ１）の含有割合が５〜３０重量部であり、上記化合物（Ｃ２）の含有割合が５〜３０重量部である上記〔１〕〜〔６〕のいずれかに記載の活性エネルギー線硬化型塗料組成物。
The present invention is as follows.
[1] (A) A (meth) acryloyl group-containing silicon compound (a1) represented by the following general formula (1) and a silicon compound (a2) represented by the following general formula (2) (A1) An organosilicon compound obtained by hydrolytic copolycondensation at a ratio of 0.3 to 1.8 mol of the silicon compound (a2) per 1 mol;

(In General Formula (1), R ¹ is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ² is 1 carbon atom. To 6 divalent saturated hydrocarbon groups, R ³ is a hydrogen atom or a methyl group, X is a hydrolyzable group, and a plurality of X may be the same or different from each other, n Is 0 or 1.)
SiY ₄ (2)
(In General Formula (2), Y is a siloxane bond-forming group, and a plurality of Y may be the same or different from each other.)
(B) a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having (meth) acrylate having two or more (meth) acryloyl groups and one or more hydroxyl groups, and polyisocyanate Adduct compound (b1) obtained by addition reaction with (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having 3 or more (meth) acryloyl groups, (Meth) acrylate mixture composed of (meth) acrylate (b2) not having
And
(C) a radically polymerizable unsaturated compound having a nitrogen atom in the molecule, which contains a compound other than the component (A) and the component (B),
The content of the component (A), the component (B) and the component (C) is 5 to 50 parts by weight of the component (A) and 100% by weight of the component (B). ) Is 30 to 90 parts by weight, and the active component (C) is 5 to 35 parts by weight.
[2] The compound (a1) is a compound in which X in the general formula (1) is an alkoxy group and n is 0.
The said compound (a2) is an active energy ray hardening-type coating composition as described in said [1] whose Y in General formula (2) is an alkoxy group.
[3] The above [1] or [2], wherein the component (C) comprises at least one compound (C1) selected from a morpholinyl group-containing monomer, an amide group-containing monomer, and a lactam compound. The active energy ray-curable coating composition described in 1.
[4] Active energy ray curing according to the above [3], wherein the compound (C1) is at least one selected from acryloylmorpholine, N-vinylformamide, N-vinylacetamide and N-vinyl-ε-caprolactam. Mold paint composition.
[5] The component (C) includes the compound (C2) having an isocyanuric ring, and the content of the compound (C2) is 5 to 30 parts by weight. Active energy ray-curable coating composition.
[6] The active energy ray-curable coating composition according to the above [5], wherein the compound (C2) is a radical polymerizable unsaturated compound modified with alkylene oxide or caprolactone.
[7] The content of the component (C) is 10 to 35 parts by weight when the total of the component (A), the component (B) and the component (C) is 100 parts by weight, Component (C) comprises a morpholinyl group-containing monomer, an amide group-containing monomer, and at least one compound (C1) selected from lactam compounds, and a compound (C2) having an isocyanuric ring, When the total of both is 10 to 35 parts by weight, the content of the compound (C1) is 5 to 30 parts by weight, and the content of the compound (C2) is 5 to 30 parts by weight [1 ] The active energy ray-curable coating composition according to any one of [6] to [6].

The composition of one embodiment of the present invention can be a composition that does not contain an organic solvent, and forms a cured film having high hardness and excellent scratch resistance with respect to various substrates such as plastics. It becomes possible to do.
In addition, according to the composition of another embodiment of the present invention, it is possible to form a cured film having high hardness and excellent scratch resistance and impact resistance on various substrates such as plastics. Become.

The active energy ray-curable coating composition of the present invention comprises the above components (A), (B) and (C) with respect to a total of 100 parts by weight.
(A) 5 to 50 parts by weight of component,
30-90 weight part of (B) component and 5-35 weight part of (C) component are contained.
Hereinafter, the detail of each component and a composition is demonstrated.
In the present specification, an acryloyl group or a methacryloyl group is represented as “(meth) acryloyl group”, and an acrylate or methacrylate is represented as “(meth) acrylate”.

（一般式（１）において、Ｒ¹は炭素数１〜６のアルキル基、炭素数７〜１０のアラルキル基又は炭素数６〜１０のアリール基を有する有機基であり、Ｒ²は炭素数１〜６の２価の飽和炭化水素基であり、Ｒ³は水素原子又はメチル基であり、Ｘは加水分解性基であり、複数のＸは互いに同一であっても異なっていても良く、ｎは０又は１である。）1. Ingredient (A)
The component (A) according to the present invention includes a (meth) acryloyl group-containing silicon compound (a1) (hereinafter referred to as “compound (a1)”) represented by the following general formula (1) and the following general formula (2). Hydrolysis of the represented silicon compound (a2) (hereinafter referred to as “compound (a2)”) at a ratio of 0.3 to 1.8 mol of the compound (a2) with respect to 1 mol of the compound (a1). It is an organosilicon compound obtained by copolycondensation.

(In General Formula (1), R ¹ is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ² is 1 carbon atom. To 6 divalent saturated hydrocarbon groups, R ³ is a hydrogen atom or a methyl group, X is a hydrolyzable group, and a plurality of X may be the same or different from each other, n Is 0 or 1.)

SiY ₄ (2)
(In General Formula (2), Y is a siloxane bond-forming group, and a plurality of Y may be the same or different from each other.)

In the general formula to indicate a compound (a1) (1), R 1 is an organic group having an alkyl group, an aralkyl group or an aryl group having 6 to 10 carbon atoms of 7 to 10 carbon atoms having 1 to 6 carbon atoms.
Among these, a C1-C6 alkyl group is preferable and a methyl group is more preferable at the point which the cured film of the composition obtained is excellent in abrasion resistance.
R ² is a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, preferably an alkylene group. As the alkylene group, a cured film of the resulting composition has excellent wear resistance, and a trimethylene group is more preferable from the viewpoint of raw material cost. R ³ is a hydrogen atom or a methyl group.
X is a hydrolyzable group, and a plurality of X may be the same as or different from each other. As the hydrolyzable group, various groups can be used as long as they are hydrolyzable groups. Specific examples include a hydrogen atom, an alkoxy group, a cycloalkoxy group, an aryloxy group, and an arylalkoxy group. Among these, an alkoxy group is preferable, and an alkoxy group having 1 to 6 carbon atoms is more preferable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.
Further, n is 0 or 1, and is preferably 0 in that the cured film of the resulting composition is excellent in wear resistance.

  In the general formula (1), specific examples of a compound where n is 0 and X is an alkoxy group are preferable compounds: 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropyltrimethoxy Examples thereof include silane and 3- (meth) acryloyloxypropylethyltriethoxysilane.

In the general formula (2) showing the compound (a2), Y is a siloxane bond-forming group, and a plurality of siloxane bond-forming groups in one molecule may be the same or different.
As the siloxane bond-forming group, an alkoxy group is preferable. Preferable examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a sec-butoxy group.
Preferred specific examples of the compound (a2) are alkoxysilane compounds having an n-propoxy group such as tetra-n-propoxysilane, trimethoxy-n-propoxysilane, dimethoxydi-n-propoxysilane, methoxytri-n-propoxysilane, and the like. .
The n-propoxy group-containing alkoxysilane compound may be a single compound or a mixture of compounds having an n-propoxy group and other alkoxy groups.
The mixture of the n-propoxy group-containing alkoxysilane compound can be used by mixing plural kinds of components, but can also be used as it is produced by alcohol exchange. For example, it can be obtained by subjecting a silicon compound represented by the above general formula (2) and having no n-propoxy group (for example, tetramethoxysilane) to alcohol exchange reaction in 1-propanol. it can. Moreover, the reaction product obtained by this reaction can also be used as it is.

  Component (A) is a compound obtained by hydrolytic copolycondensation of compound (a1) and compound (a2) at a ratio of 0.3 to 1.8 mol of compound (a2) with respect to 1 mol of compound (a1). (Hereinafter referred to as “first step”). The reaction conditions for the hydrolytic copolycondensation are not particularly limited, but are preferably alkaline conditions. Hereinafter, the first step under alkaline conditions will be described.

The reaction ratio of the compound (a1) to the compound (a2) is 0.3 to 1.8 mol of the compound (a2) with respect to 1 mol of the compound (a1), preferably 0.8% of the compound (a2). More preferably, compound (a2) is 1-1.4 mol in a ratio of -1.6 mol. By reacting at this ratio, the component (A) can be efficiently produced without causing gelation during and after the reaction.
By proceeding the first step under alkaline conditions, gelation after the reaction can be prevented, and the component (A) can be produced in a high yield.
Specifically, the alkaline condition is such that the pH of the reaction system exceeds 7, preferably 8 or more, more preferably 9 or more. The upper limit is usually pH 13. By setting the reaction system to the above pH, the component (A) having excellent storage stability can be produced in a high yield.
An organosilicon compound obtained by hydrolytic copolycondensation under acidic conditions (less than pH 7) may be inferior in storage stability.
Further, under neutral conditions (around pH 7), the hydrolysis copolycondensation reaction may hardly proceed.

  In the first step, the condensation rate of the compound (a1) and the compound (a2) can be 92% or more, more preferably 95% or more, and still more preferably 98% or more. Most preferably, the siloxane bond-forming groups (including hydrolyzable groups) are substantially all condensed, but the upper limit of the condensation rate in the first step is usually 99.9%.

Conventionally, a method for producing an organosilicon compound under acidic conditions is known, but it is difficult to uniformly react both the compound (a1) and the compound (a2) of the raw material compound, and a gel is likely to be generated. . Therefore, a method of avoiding gelation by causing a silicon compound having only one siloxane bond-forming group (hereinafter referred to as “M monomer”), such as trimethylalkoxysilane or hexamethyldisiloxane, to act as an end-capping agent. It has been known.
However, even when gelation can be avoided by using a predetermined amount or more of the M monomer, the inorganic properties of the resulting organosilicon compound tend to decrease.
On the other hand, according to the production method under alkaline conditions, the compound (a1) and the compound (a2) can be copolycondensed without gelation, and the inorganic properties of the resulting cured product can be reduced. There is no effect.

The component (A) is produced by using the first step as an essential component, but the production method of the component (A) can further include the following steps as necessary.
(Second step) A step of neutralizing the reaction solution obtained in the first step with an acid.
(Third step) A step of removing volatile components from the neutralized liquid obtained in the second step.
(Fourth step) A step of mixing and contacting the concentrate obtained in the third step with a cleaning organic solvent to dissolve at least the component (A) in the cleaning organic solvent.
(5th process) The process of obtaining the organic solution containing a component (A), after wash | cleaning the organic type liquid obtained at the 4th process with water.
(Sixth Step) A step of removing volatile components from the organic solution obtained in the fifth step.
It is preferable that the manufacturing method of a component (A) includes a 1st process, a 2nd process, and a 5th process.

  In the production of the component (A), the reaction system of the first step, the reaction solution containing the component (A) after the first step, the neutralization solution after the second step, the organic solution after the fourth step, and the fifth step A polymerization inhibitor that inhibits polymerization of the (meth) acryloyl group may be added to at least one of the later organic solutions.

The content ratio of the component (A) in the composition of the present invention is 5 to 50 parts by weight, preferably 5 to 5 parts, when the total of the components (A), (B) and (C) is 100 parts by weight. 40 parts by weight, more preferably 10 to 35 parts by weight.
By making the content rate of a component (A) into 5 to 50 weight part, it can be set as the composition which gives the cured film excellent in hardness and scratch resistance.

2. Ingredient (B)
Component (B) according to the present invention is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having two or more (meth) acryloyl groups and one or more hydroxyl groups ( Urethane adduct compound (b1) obtained by addition reaction of (meth) acrylate and polyisocyanate (hereinafter referred to as “component (b1)”) and (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol And a (meth) acrylate mixture composed of (meth) acrylate (b2) (hereinafter referred to as “component (b2)”) having 3 or more (meth) acryloyl groups and no hydroxyl group. .

The raw material compound of component (b1) is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having two or more (meth) acryloyl groups and one or more hydroxyl groups (meta) ) Acrylate (hereinafter referred to as “hydroxyl-containing polyfunctional (meth) acrylate”).
Various compounds can be used as the trihydric or higher aliphatic polyhydric alcohol which is a raw material compound of a hydroxyl group-containing polyfunctional (meth) acrylate, and examples include trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol. .
As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, specifically, trimethylolpropane di (meth) acrylate, pentaerythritol di- or tri (meth) acrylate, ditrimethylolpropane di- or tri- Examples include (meth) acrylate and dipentaerythritol di, tri, tetra, or penta (meth) acrylate.
Among these, a compound having three or more (meth) acryloyl groups and one hydroxyl group is preferable in that the cured film is excellent in hardness and scratch resistance. Specifically, pentaerythritol tri (meth) is preferable. Examples include acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

Various compounds can be used as polyisocyanate, which is another synthetic raw material for component (b1).
Examples of preferred polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 2,4-tolylene diisocyanate, and their nurate type trimers.

  The component (b1) is synthesized by an addition reaction between a hydroxyl group-containing polyfunctional (meth) acrylate and a polyisocyanate. Although this addition reaction can be performed without a catalyst, the reaction may be carried out in the presence of a catalyst such as a tin compound such as dibutyltin dilaurate or an amine compound such as triethylamine in order to advance the reaction efficiently.

Component (b2) is a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol.
As the trivalent or higher aliphatic polyhydric alcohol which is a raw material compound of the component (b2), the same as those mentioned above can be used.
Specific examples of the component (b2) include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
Among these, a compound having four or more (meth) acryloyl groups is preferable in that the cured film is excellent in wear resistance and scratch resistance. Specifically, pentaerythritol tetra (meth) acrylate and ditrimethylol are preferable. Examples include propanetetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Component (B) according to the present invention is a mixture of components (b1) and (b2).
The ratio of components (b1) and (b2) may be set as appropriate according to the purpose. The component (B) is preferably a mixture containing (b1) :( b2) = 10: 90 to 75:25, more preferably (b1) :( b2) = 30: 70 to 70: It is a mixture containing at a weight ratio of 30.
By setting the weight ratio of components (b1) and (b2) within this range, a composition that gives a cured film having excellent hardness and scratch resistance can be obtained.

The content ratio of the component (B) in the composition of the present invention is 30 to 90 parts by weight, preferably 40 to 90 parts by weight with respect to 100 parts by weight of the total of the components (A), (B) and (C). Part, more preferably 50 to 85 parts by weight.
By making the content rate of a component (B) into 30-90 weight part, it can be set as the composition which gives the cured film excellent in hardness and scratch resistance.

3. Ingredient (C)
The component (C) according to the present invention is a radically polymerizable unsaturated compound having a nitrogen atom in the molecule (hereinafter also referred to as “unsaturated compound (C)”), and the component (A) and the component ( Compounds other than B).
By using the unsaturated compound (C), it is possible to obtain an active energy ray-curable coating composition that gives a cured film having excellent hardness and scratch resistance. Moreover, when it contains the specific compound (C1) mentioned later, it can be set as a composition whose viscosity is low enough, and when it contains the specific compound (C2) mentioned later, hardness and scratch resistance The impact resistance of the cured film can be improved without lowering.

In the present invention, the number of radically polymerizable unsaturated groups that the unsaturated compound (C) has is not particularly limited, but when the viscosity of the composition is relatively low, a compound having one radically polymerizable unsaturated group So-called monofunctional unsaturated compounds are preferred.
Specific examples of such monofunctional unsaturated compounds include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-methoxy. Such as methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropyl acrylamide, N-vinylformamide, N-vinylacetamide, diacetone (meth) acrylamide, etc. Amide group-containing monomer; Amino group-containing monomer such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate; N-vinylpyrrolidone; N-vinyl-ε -Caprolactam Lactam compound of; (meth) acrylate morpholinyl group-containing monomers such as acryloyl morpholine, (meth) acrylonitrile, N- cyclohexyl maleimide, N- phenylmaleimide, and the like. These compounds may be used independently and may use 2 or more types together.

  Among these, the amide group-containing monomer, the lactam compound, and the morpholinyl group-containing monomer (hereinafter referred to as these) from the point that the Tg of the homopolymer is high and the hardness and scratch resistance of the resulting cured film are good. Are referred to as “compound (C1)”. As this compound (C1), dimethyl (meth) acrylamide, N-vinylformamide, N-vinylacetamide, and (meth) acryloylmorpholine are more preferable. Among these, N-vinylformamide and N-vinylacetamide, which are amide group-containing monomers, are more preferable because they have a high effect of reducing not only the performance of the cured product but also the viscosity of the composition.

  The unsaturated compound (C) is a radically polymerizable unsaturated compound having an isocyanuric ring in the molecule (hereinafter also referred to as “compound (C2)”) alone or in combination with the compound (C1). Preferred component. And as this compound (C2), isocyanuric acid EO modified | denatured di (meth) acrylate, isocyanuric acid EO modified | denatured tri (meth) acrylate, and these mixtures (For example, Toagosei Co., Ltd. make " Alkylene oxide modified (meth) acrylates such as “Aronix M-313” and “Aronix M-315”, “Funkryl FA-731A” manufactured by Hitachi Chemical Co., Ltd., “NK Ester A-9300” manufactured by Shin-Nakamura Chemical Co., Ltd., etc.) Ε-caprolactone-modified tris [2- (meth) acryloxyethyl] isocyanurate (for example, “Aronix M-327” manufactured by Toagosei Co., Ltd., “NK Ester A manufactured by Shin-Nakamura Chemical Co., Ltd.); Ε-caprolactone-modified (meth) acrylates such as “-9300-1CL”; A reaction product of a trimer of a bifunctional isocyanate such as tylene diisocyanate and isophorone diisocyanate and a hydroxyl group-containing (meth) acrylate (as a specific product name, for example, “Art Resin UN-905” manufactured by Negami Kogyo Co., Ltd.), Esterified product of 1,3-bis (2-carboxyethyl) isocyanurate and 2-hydroxyethyl (meth) acrylate, tri (meth) acrylic acid ester of tris (2-hydroxyethyl) isocyanurate, other isocyanuric acid derivatives (Specific product names include “MA-DGIC”, “DA-MGIC”, “MeDAIC”, “AcDGIC”, etc., manufactured by Shikoku Kasei Co., Ltd.). These compounds may be used alone or in combination of two or more.

As the compound (C2), alkylene oxide-modified (meth) acrylates and ε-caprolactone-modified (meth) acrylates are more preferable because the resulting cured film has better impact resistance.
The number of radically polymerizable unsaturated groups that the compound (C2) has is not particularly limited, and may be one or two or more. In the present invention, a compound having two or more radically polymerizable unsaturated groups is preferred because a cured film having high hardness and good scratch resistance can be easily obtained.

The content of the unsaturated compound (C) in the composition of the present invention is 5 to 35 parts by weight, preferably 100 parts by weight of the total of components (A), (B) and (C), preferably It is 5-30 weight part, More preferably, it is 8-25 weight part.
By containing 5 to 35 parts by weight of the unsaturated compound (C), a cured film having excellent hardness and scratch resistance can be obtained.

In the present invention, when the unsaturated compound (C) comprises only the compound (C1), the viscosity of the composition is reduced to such an extent that it can be applied without containing an organic solvent. When the total of (A), (B) and (C) is 100 parts by weight, it is preferably 5 to 35 parts by weight, more preferably 5 to 30 parts by weight, still more preferably 8 to 25 parts by weight.
When the unsaturated compound (C) consists only of the compound (C2), a cured film having better impact resistance can be obtained. Therefore, the content ratio of the components (A), (B) and (C) When the total is 100 parts by weight, it is preferably 5 to 30 parts by weight, more preferably 8 to 30 parts by weight, still more preferably 10 to 25 parts by weight.

  Further, when the unsaturated compound (C) is composed of the compounds (C1) and (C2), a cured film excellent in all of hardness, scratch resistance and impact resistance can be obtained. Therefore, a preferable content ratio of these compounds Is shown below. When the total of both is 10 to 35 parts by weight, the content ratio of the compound (C1) is preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight, still more preferably 8 to 25 parts by weight. The content ratio of the compound (C2) is preferably 5 to 30 parts by weight, more preferably 8 to 30 parts by weight, and still more preferably 10 to 25 parts by weight. By setting the content ratio of the compound (C1) to 5 to 30 parts by weight, the viscosity of the composition is reduced to such an extent that it can be applied without using an organic solvent, and the hardness, scratch resistance and impact resistance are excellent. A cured film can be obtained.

4). Active energy ray-curable coating composition The active energy ray-curable coating composition of the present invention may be either a composition containing an organic solvent or a composition not containing an organic solvent, and depending on the type of component (C), It can also be set as the composition containing an organic solvent. For example, when component (C) contains compound (C1), it can be set as the composition which does not contain an organic solvent. Moreover, when a component (C) contains a compound (C2) or when both a compound (C1) and (C2) are included, it is preferable to contain an organic solvent. Usable organic solvents will be described later.

  The composition of the present invention essentially comprises the components (A), (B) and (C), but depending on the purpose, a photopolymerization initiator, a pigment, a dye, a surface conditioner, and an ultraviolet absorber. Various components such as an agent, a light stabilizer such as HALS, a compound having a radical polymerizable unsaturated group other than components (A), (B) and (C), and an organic polymer can also be blended.

  As the photopolymerization initiator, various compounds can be used, and specific examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2- Hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, diethoxyacetophenone , Oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2 Acetophenone compounds such as hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methyl-propan-1-one; benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'- Benzophenone compounds such as methyl-diphenylsulfide; methylbenzoylformate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid Α-ketoester compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) Phosphine oxide compounds such as -2,4,4-trimethylpentylphosphine oxide; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; Acetophenone / benzophenone hybrid photoinitiators such as 4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime)- Examples include oxime ester photopolymerization initiators such as 1- [4- (phenylthio)]-1,2-octanedione; and camphorquinone.

The preferable compounding amount of the photopolymerization initiator is 0.1 to 10 parts by weight, more preferably 0.5 to 100 parts by weight when the total of components (A), (B) and (C) is 100 parts by weight. 7 parts by weight, particularly preferably 1 to 5 parts by weight.
By setting the blending amount of the photopolymerization initiator to 0.1 to 10 parts by weight, the composition has excellent curability and can be a composition that gives a cured film having excellent hardness and scratch resistance.

  The surface conditioner has an effect of enhancing leveling properties when the composition of the present invention is applied, an effect of enhancing the antifouling property and slipperiness of the cured coating film, and the like. As the surface conditioner, a silicone-based surface conditioner or a fluorine-based surface conditioner is suitable. Specific examples include a silicone polymer having a silicone chain and a polyalkylene oxide chain, a fluorine polymer having a perfluoroalkyl group and a polyalkylene oxide chain, and a fluorine polymer having a perfluoroalkyl ether chain and a polyalkylene oxide chain. Can be mentioned.

  The preferable compounding amount of the surface conditioner is 0.01 to 3 parts by weight, more preferably 0.02 to 0 when the total of components (A), (B) and (C) is 100 parts by weight. .5 parts by weight. By setting the blending amount to 0.01 parts by weight or more, the surface smoothness of the coating film can be improved and the generation of bubbles during application can be suppressed.

The compound having another radical polymerizable unsaturated group is not particularly limited as long as it is a compound having at least one radical polymerizable unsaturated group in one molecule.
Specific examples of the compound having one radical polymerizable unsaturated group in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, styrene, 2-hydroxypropyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylate of an alkylene oxide adduct of phenol, (meth) acrylate of an alkylene oxide adduct of alkylphenol, and the like.

In addition, a compound having two or more radically polymerizable unsaturated groups in one molecule (hereinafter referred to as “other polyfunctional unsaturated compound”) improves adhesion, hardness and scratch resistance to the substrate. Can do.
The number of radically polymerizable unsaturated groups in the other polyfunctional unsaturated compound is preferably 3 to 20 per molecule from the viewpoint of not reducing the hardness and scratch resistance.

As another polyfunctional unsaturated compound, a compound having two or more (meth) acryloyl groups in one molecule is preferable.
Specific examples include di (meth) acrylate of an alkylene oxide adduct of bisphenol A, di (meth) acrylate of an alkylene oxide adduct of bisphenol F, di (meth) acrylate of an alkylene oxide adduct of bisphenol Z, and bisphenol S. Di (meth) acrylate of alkylene oxide adduct, di (meth) acrylate of alkylene oxide adduct of thiobisphenol, di (meth) acrylate of bisphenol A, di (meth) acrylate of bisphenol F, di (meth) of bisphenol Z Acrylate, di (meth) acrylate of bisphenol S, di (meth) acrylate of thiobisphenol, tricyclodecane dimethylol di (meth) acrylate, ethylene glycol di (meth) acrylate Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, glycerol di (meth) acrylate, di (meth) acrylate of alkylene oxide adduct of glycerol, dimer acid diol di (meth) acrylate, cyclohexane dimethylol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, trimethylolpropane alkylene oxide adduct tri (meth) acrylate, pentaerythritol tri- and tetraacrylate, pentaerythritol Alkylene oxide adduct tri- and tetraacrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa and pentaacrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, Examples thereof include silicone resins having a (meth) acryloyl group.

  Among these, as polyester (meth) acrylate, the dehydration condensate of polyester polyol and (meth) acrylic acid is mentioned. Polyester polyols include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, and trimethylolpropane, or Reaction products obtained using these polyol components such as alkylene oxide adducts and acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or anhydrides thereof And dehydration condensates of various dendrimer type polyols with (meth) acrylic acid.

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

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

  An organic polymer has the effect | action which reduces the curvature at the time of hardening, maintaining transparency. A suitable organic polymer is a (meth) acrylic polymer, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- (2 -(Meth) acryloxyethyl) tetrahydrophthalimide and the like. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.

  Even if the composition of the present invention does not contain an organic solvent, it may be excellent in coating properties and handling properties, but for the purpose of further improving these performances, or for the purpose of adjusting the viscosity of the composition, Organic solvents can be used. As an organic solvent, what dissolve | melts component (A), (B) and (C) is preferable.

  Specific examples of preferred organic solvents include alcohols such as ethanol and isopropanol; alkylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; aromatic compounds such as toluene and xylene; Examples include ester compounds such as glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether; N-methylpyrrolidone and the like.

A preferable blending amount of the organic solvent is 10 to 1000 parts by weight, more preferably 50 to 500 parts by weight, further preferably 100 parts by weight when the total of components (A), (B) and (C) is 100 parts by weight. Is 50 to 300 parts by weight.
Since the viscosity of the curable composition is sufficiently reduced by setting the blending amount of the organic solvent to 10 to 1000 parts by weight, a known coating method (bar coating, roll coating, spin coating, dip coating, gravure coating, die coating, It is easy to prepare a coating composition corresponding to flow coat, spray coat, etc.

  The viscosity (25 ° C.) measured by the E-type viscometer of the active energy ray-curable coating composition of the present invention is preferably 20,000 mPa · s or less, more preferably 15,000 mPa · s, from the viewpoint of coating properties. s or less, more preferably 10,000 mPa · s or less. The lower limit is usually 100 mPa · s.

  The production method of the active energy ray-curable coating composition of the present invention may be in accordance with a conventional method. Component (A), Component (B), Component (C), and other components used as necessary Can be made into a manufacturing method provided with processes, such as stirring and mixing.

5. Coating method The active energy ray-curable coating composition of the present invention is suitable for forming a coating film having high adhesion to a substrate.
The composition of the present invention can be applied to a substrate made of various materials. And as a preferable base material, wood, a metal, an inorganic material, a plastics, etc. are mentioned.
Examples of the inorganic material include mortar, concrete, and glass.
Specific examples of the plastic include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride, polycarbonate resins, epoxy resins, and polyurethane resins.

The method for coating the base material with the composition of the present invention is not particularly limited, and may be a conventional method. For example, bar coating, roll coating, spin coating, dip coating, gravure coating, flow coating, spray coating, and the like can be applied.
Moreover, as a specific method of forming the cured film, there may be mentioned a method of irradiating the coating film with active energy rays after applying the composition to the substrate. In addition, you may pass through the drying process or preheating process of a coating film before irradiation of an active energy ray as needed.

The coating film and the film thickness after drying may be appropriately set according to the purpose, but are generally about 5 to 300 μm.
The drying temperature or preheating temperature is not particularly limited as long as the applied substrate is at a temperature that does not cause problems such as deformation.

Examples of active energy rays for curing the coating film made of the composition of the present invention include electron beams, ultraviolet rays, visible rays, and X-rays, but ultraviolet rays are preferable because inexpensive devices can be used. .
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED.
The irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm ² is preferable, and 200 to 1,000 mJ / cm ² is more preferable.
In the case of curing with an electron beam, various devices can be used as an electron beam (EB) irradiation device that can be used, for example, Cockloft-Waltsin type, Bandegraph type, and resonance transformer type devices. The electron beam is preferably one that gives an energy of 50 to 1,000 eV, more preferably 100 to 300 eV.

The cured film obtained by using the composition of the present invention is excellent in hardness and scratch resistance. For example, the pencil hardness measured according to JIS K 5600-5-4 is usually 8H or more, and damage due to contact with a metal member or the like is also suppressed. The material having the cured film can be used for various applications by taking advantage of this characteristic.
For example, the display panel front plate, building material applications, lighting fixtures, displays and cases such as mobile phones and smartphones, home appliance cases, and various lenses such as glasses.
Specific examples of the front plate for the display board include an electric bulletin board, a display, a signboard, an advertisement, and a sign.
Examples of using wood as a base material include woodwork products such as stairs, floors and furniture. Examples of using metal as the substrate include metal products such as kitchen panels for kitchens and stainless steel sinks.

Hereinafter, the present invention will be specifically described based on examples. In addition, this invention is not limited by these Examples.
In the following, “part” means part by weight, and “%” means percent by weight.

1. Production of Component (A) Production Example 1 (Production of MAC-TQ)
A reactor equipped with a stirrer and a thermometer was charged with 150 g of 1-propanol for alcohol exchange reaction and 36.53 g (0.24 mol) of tetramethoxysilane (hereinafter referred to as “TMOS”), and then stirred. Then, 4.37 g of a 25% tetramethylammonium hydroxide methanol solution (0.1 mol of methanol, 12 mmol of tetramethylammonium hydroxide) was gradually added and reacted at a temperature of 25 ° C. and pH 9 for 6 hours. Thereafter, the internal temperature was set to 60 ° C., and the reaction was further continued for 1 hour with stirring. Here, when the reaction solution was subjected to gas chromatographic analysis (TCD detector), 1 to 4 of methoxy groups contained in TMOS were substituted with n-propoxy group, 1-substituted product, 2-substituted product, 3-substituted product or 4 Substituted compounds and unreacted TMOS were detected. Only trace amounts of TMOS were detected. Among these, the ratio of the n-propoxy group-containing compound (n-propoxy group-containing alkoxysilane) was almost 100% in total. Based on the peak area of the product in the gas chromatogram, the number of 1-propanol substitutions (average of the number of n-propoxy groups per molecule of n-propoxy group-containing compound) was determined to be 2.7.
Next, 59.62 g (0.24 mol) of 3-methacryloxypropyltrimethoxysilane was added to the reaction solution, and 30.2 g of water was further added. Then, 7.88 g of a 25% tetramethylammonium hydroxide methanol solution (0.18 mol of methanol, 21.6 mmol of tetramethylammonium hydroxide) was added and reacted for 24 hours at a temperature of 25 ° C. and a pH of 9 while stirring. . Thereafter, 22.2 g (35.3 mmol) of a 10% nitric acid aqueous solution was added for neutralization. Next, this neutralized solution was added to a mixed solution of 120 g of diisopropyl ether and 180 g of water for extraction. The diisopropyl ether layer is washed with water to remove salts and excess acid, and then N-nitrosophenylhydroxylami aluminum salt “Q-1301” (trade name) manufactured by Wako Pure Chemical Industries, Ltd. is used as a polymerization inhibitor. .5 mg was added. From the obtained diisopropyl ether solution, the organic solvent was distilled off under reduced pressure to obtain a colorless and transparent solid organosilicon compound (hereinafter referred to as “MAC-TQ”). The yield was 57.72g.

As a result of ¹ H-NMR analysis of MAC-TQ, the 3-methacryloxypropyltrimethoxysilane used as the compound (a1) and the n-propoxy group-containing alkoxysilane used as the compound (a2) stoichiometrically. It was confirmed to be a copolycondensate obtained by reaction.
The content ratio of the alkoxy group (n-propoxy group bonded to the silicon atom) calculated from the ¹ H-NMR chart of MAC-TQ corresponds to 2.5% with respect to the entire alkoxy group contained in the raw material. It was the amount to be.
Moreover, when the average molecular weight of MAC-TQ was measured by gel permeation chromatography (GPC), Mn of the standard polystyrene conversion was 9,600.

2. Production of Component (B) Production Example 2 (Production of HDI-M305)
In a 0.5 L separable flask equipped with a stirrer and an air blowing tube, a mixture of pentaerythritol triacrylate (hereinafter referred to as “PETri”) and pentaerythritol tetraacrylate (hereinafter referred to as “PETet”) (PETri0.3). "Aronix M-305" (trade name, hereinafter referred to as "M-305") manufactured by Toagosei Co., Ltd., 2,6-di-tert-butyl 0.092 g of -4-methylphenol (hereinafter referred to as “BHT”) and 0.055 g of dibutyltin dilaurate (hereinafter referred to as “DBTL”) were charged and the liquid temperature was adjusted to 70 to 75 ° C., and these were stirred. , 25.2 g (0.15 mol) of hexamethylene diisocyanate (hereinafter referred to as “HDI”) ) Was added dropwise and reacted.
After completion of the dropwise addition of HDI, the reaction was further continued at an internal temperature of 80 ° C. and stirred for 3 hours. The reaction was completed after confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product. Hereinafter, this reaction product is referred to as “HDI-M305”.

  HDI-M305 includes a urethane adduct compound (b1) that is a reaction product of PETri and HDI, and PETet that does not react with HDI (corresponding to compound (b2)), and the weight ratio is (b1) :( b2) = 6: 4 containing mixture.

3. Production and evaluation of active energy ray curable coating composition Using the MAC-TQ and HDI-M305 obtained above and the components shown in Table 1, an active energy ray curable coating composition was produced and evaluated in various ways. It was used for.

Example 1-1 to Example 1-4 and Comparative Examples 1-1 to 1-4
Each raw material was used in the proportions shown in Table 2 and stirred and mixed at room temperature according to a conventional method to prepare an active energy ray-curable coating composition.
Thereafter, the viscosity of each composition obtained at 25 ° C. was measured with an E-type viscometer, and the obtained values were listed in each table.

Thereafter, each composition was hung on the surface of one side of a 7 cm × 15 cm × 50 μm polyethylene terephthalate film, and a 50 μm-thick release film made of polyethylene terephthalate and transmitting ultraviolet rays was placed thereon. It was. Subsequently, it passed through the laminating roll so that the film thickness after curing was about 50 μm, and the thickness of the coating film was adjusted. A coating film was formed on the other surface of the polyethylene terephthalate film in the same manner. Then, the cured film was created on both surfaces of the polyethylene terephthalate film by irradiating with ultraviolet rays through the release film under the following conditions.
For ultraviolet irradiation, an ultraviolet ray irradiator (high pressure mercury lamp) manufactured by Eye Graphics Co., Ltd. was used, and irradiation was performed one pass on each side at a lamp height of 19 cm and a conveyor speed of 2.3 m / min. The irradiation energy per pass was measured with a photometer “UV POWER PUCK” manufactured by EIT, and found to be 900 mJ / cm ² in the UV-A region. The peak illuminance was 170 mW / cm ² in the UV-A region.
About the obtained cured film, pencil hardness, abrasion resistance, and adhesiveness were evaluated by the method shown below. The evaluation results are shown in Table 2.

(1) Pencil hardness Pencil hardness was measured according to JIS K 5600-5-4.

(2) Scratch resistance The number of scratches when rubbing 400 reciprocating times while applying a load of 1200 g / 4 cm ^{2 to} the surface of the cured film with steel wool “Bonster # 0000” manufactured by Nippon Steel Wool Co., Ltd. Was measured. Using the number of scratches, scratch resistance was evaluated based on the following criteria. Here, the evaluation “A” or “B” was defined as good scratch resistance.
A: There was no scratch.
B: There were 1 to 9 scratches.
C: There were 10 or more scratches.

  Each composition of Examples 1 to 5 showed a viscosity of 10,850 mPa · s or less, even though no organic solvent was used, and the viscosity was sufficiently reduced to a degree capable of being applied. Moreover, it was confirmed that the cured film shows a good pencil hardness of 8H to 10H, is excellent in wear resistance, and is excellent in scratch resistance. Among them, Examples 3 to 5 using N-vinylformamide (NVF) as the component (C) have a reduced viscosity of the composition, which is advantageous for coating properties during various coatings. It was.

On the other hand, since Comparative Example 1 does not contain the component (C) according to the present invention, it has a very high viscosity of 34,400 mPa · s, and is diluted with an organic solvent or the like at the time of handling and coating. It was highly necessary. Moreover, in Comparative Example 2 using 1,6-hexanediol diacrylate (HDDA), which is an unsaturated compound not containing a nitrogen atom, both the pencil hardness and the scratch resistance of the cured film were reduced.
Comparative Examples 3 and 4 are experimental examples when the content of the component (C) according to the present invention is outside the range defined in the present invention. In Comparative Example 3 in which the content of the component (C) is too small, the viscosity of the composition cannot be sufficiently reduced. Conversely, in Comparative Example 4 in which the content of the component (C) is too large, the pencil of the cured film is used. Hardness and scratch resistance were low.

Examples 6 to 11 and Comparative Example 5
Using each raw material shown in Table 3 in the ratio shown in Table 3, the active energy ray-curable coating composition was prepared by stirring and mixing at room temperature according to a conventional method. The composition of Comparative Example 5 is the same as the composition of Comparative Example 1. The viscosity of each composition was measured, and the coating suitability was determined according to the criteria classified as follows. The results are also shown in Table 3.
A: The viscosity was 100 mPa · s to 10,000 mPa · s B: The viscosity was more than 10,000 mPa · s to 15,000 mPas or less C: The viscosity was more than 15,000 mPa · s to 20, D: Viscosity exceeded 20,000 mPa · s. Thereafter, in the same manner as in Example 1, cured films were formed on both surfaces of the polyethylene terephthalate film. In addition to the above (1) hardness and (2) scratch resistance, the following (3) impact resistance was evaluated. These evaluation results are shown in Table 3.

(3) Impact resistance (falling ball test)
A 25 g iron ball according to JIS B 1501 was dropped from a height of 10 cm on the surface of the cured film. When no cracks or cracks occurred in the cured film, the operation of raising the height by 5 cm and dropping the iron ball was repeated, and the maximum height at which no cracks or cracks occurred was recorded. This test was conducted on five cured products, and the impact resistance was evaluated by calculating the average value of the highest values at which no cracks or cracks occurred.
The test was conducted under constant temperature and humidity conditions of 23 ° C. and 50% RH.

  The compositions of Examples 6 to 11 were also sufficiently reduced in viscosity to the extent that they could be applied. Furthermore, it was confirmed that all of the obtained cured films exhibited good pencil hardness of 8H to 10H, and were excellent in scratch resistance and impact resistance (falling ball test). In particular, in Examples 9 to 11 using two types including NVF as the component (C), the viscosity of the composition was low, and the coating operation was easy.

On the other hand, Comparative Example 5 is an experimental example of a composition that does not contain the component (C) according to the present invention. The viscosity of the composition is high, and the obtained cured film has excellent hardness and scratch resistance, but a falling ball test. The value of was as low as 15 cm and was inferior in impact resistance.

  The active energy ray-curable coating composition of the present invention can be suitably used for coating various substrates such as wood, metal, inorganic material, and plastic.

Claims (8)

(A) A (meth) acryloyl group-containing silicon compound (a1) represented by the following general formula (1) and a silicon compound (a2) represented by the following general formula (2) are converted into the silicon compound (a1). An organosilicon compound obtained by hydrolytic copolycondensation at a ratio of 0.3 to 1.8 mol of the silicon compound (a2) with respect to 1 mol;

(In General Formula (1), R ¹ is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ² is 1 carbon atom. To 6 divalent saturated hydrocarbon groups, R ³ is a hydrogen atom or a methyl group, X is a hydrolyzable group, and a plurality of X may be the same or different from each other, n Is 0 or 1.)
SiY ₄ (2)
(In General Formula (2), Y is a siloxane bond-forming group, and a plurality of Y may be the same or different from each other.)
(B) a (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having (meth) acrylate having two or more (meth) acryloyl groups and one or more hydroxyl groups, and polyisocyanate Adduct compound (b1) obtained by addition reaction with (meth) acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, having 3 or more (meth) acryloyl groups, (Meth) acrylate mixture composed of (meth) acrylate (b2) not having
And
(C) a radically polymerizable unsaturated compound having a nitrogen atom in the molecule, which contains a compound other than the component (A) and the component (B),
Content of the said component (A), the said component (B), and the said component (C) is 5-50 weight part of said component (A), when said sum total is 100 weight part, and said component (B) ) Is 30 to 90 parts by weight, and the active energy ray-curable coating composition is the component (C) is 5 to 35 parts by weight. The compound (a1) is a compound in which X in the general formula (1) is an alkoxy group and n is 0,
2. The active energy ray-curable coating composition according to claim 1, wherein in the compound (a2), Y in the general formula (2) is an alkoxy group.   The active energy ray according to claim 1 or 2, wherein the component (C) includes at least one compound (C1) selected from a morpholinyl group-containing monomer, an amide group-containing monomer, and a lactam compound. A curable coating composition.   The active energy ray-curable coating composition according to claim 3, wherein the compound (C1) is at least one selected from acryloylmorpholine, N-vinylformamide, N-vinylacetamide, and N-vinyl-ε-caprolactam. . The active energy ray-curable coating composition according to claim 4, wherein the compound (C1) contains at least N-vinylformamide. The active energy ray-curable coating composition according to claim 1 , wherein the component (C) includes a compound (C2) having an isocyanuric ring, and the content of the compound (C2) is 5 to 30 parts by weight. . The active energy ray-curable coating composition according to claim 6 , wherein the compound (C2) is a radically polymerizable unsaturated compound modified with alkylene oxide or caprolactone. The content of the component (C) is 10 to 35 parts by weight when the total of the component (A), the component (B) and the component (C) is 100 parts by weight,
The component (C) consists of at least one compound (C1) selected from morpholinyl group-containing monomers, amide group-containing monomers, and lactam compounds, and a compound (C2) having an isocyanuric ring. When the total of both is 10 to 35 parts by weight, the content of the compound (C1) is 5 to 30 parts by weight, and the content of the compound (C2) is 5 to 30 parts by weight. The active energy ray-curable coating composition according to any one of 1 to 7 .