JP2005330439A - Coating agent composition, coating product prepared by curing the same, and antifogging sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating agent composition which can give a coating capable of well-balancedly exhibiting antifogging performance, water-resistance, adhesion, weather resistance, and scratch resistance, to provide a coating prepared by curing the same, and to provide an antifogging sheet. <P>SOLUTION: The coating agent composition comprises a polyalkylene glycol urethane-modified poly(meth)acrylate and a urethane-modified poly(meth)acrylate. The polyalkylene glycol urethane-modified poly(meth)acrylate is obtained by reacting a first reaction material containing a polyisocyanate compound, a polyalkylene glycol, and a compound having a (meth)acryloyl group and a hydroxyl group by using a urethanization catalyst. The urethane-modified poly(meth)acrylate is obtained by reacting a second reaction material containing a polyisocyanate compound and a compound having a (meth)acryloyl group and a hydroxyl group by using a urethanization catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a coating composition used as an antifogging sheet or the like attached to a window glass, a lens, a mirror or the like, a coating obtained by curing the coating composition, and an antifogging sheet. More specifically, the present invention relates to a coating composition that provides a coating excellent in antifogging performance, water resistance, adhesion, weather resistance and scratch resistance, a coating obtained by curing the coating, and an antifogging sheet.

  Conventionally, when the surface temperature of a synthetic resin molded product, glass, or the like falls below the dew point temperature, there is a problem that moisture in the atmosphere is condensed into fine water droplets, resulting in cloudiness. In order to prevent such fogging, various proposals have conventionally been made for providing antifogging performance by coating a hydrophilic composition on the surface of a synthetic resin molded article or glass.

As such a composition, for example, a coating composition containing polyethylene glycol urethane-modified poly (meth) acrylate as a main component or a coating composition containing polyethylene glycol urethane-modified (meth) acrylate and a polymerizable monomer is known. (For example, see Patent Documents 1 to 3).
JP-A-5-17740 (Pages 2, 3, and 6) JP-A-9-227822 (Pages 2, 3, and 7) JP-A-6-145274 (Pages 2 and 3)

  In the coating composition disclosed in Patent Documents 1 to 3 above, polyethylene glycol urethane-modified poly (meth) acrylate is used substantially alone, and has antifogging performance, water resistance, scratch resistance, adhesion performance, and the like. Demonstrating. In this case, it is thought that anti-fogging performance is exhibited mainly by the polyoxyalkylene group, and water resistance performance, scratch resistance performance, etc. are exhibited based on the cross-linked structure of the polyfunctional monomer. However, the anti-fogging performance and other performances such as water resistance, scratch resistance, and adhesion performance are not well balanced, and individual performances have not been sufficiently exhibited.

  This is because, since the coating composition is composed only of polyethylene glycol urethane-modified poly (meth) acrylate, after the coating composition is cured, a cross-linked structure is formed as an integral structure, and on the coating object side. This is presumably because the adhesion performance and the antifogging performance on the surface side are separated and not fully expressed. Thus, in the conventional coating composition, it was not possible to exert all the performances of anti-fogging performance, water resistance performance, adhesion performance, weather resistance performance and scratch resistance performance in a well-balanced manner.

  The present invention has been made paying attention to such problems existing in the prior art. The purpose is to provide a coating composition that provides a coating capable of exhibiting a good balance of antifogging performance, water resistance performance, adhesion performance, weather resistance performance and scratch resistance performance, and a coating and antifogging sheet obtained by curing the coating composition. It is to provide.

  In order to achieve the above object, the coating composition of the first invention in the present invention comprises a first reaction raw material containing a polyisocyanate compound, a polyalkylene glycol, and a compound containing a (meth) acryloyl group and a hydroxyl group. A urethanization catalyst comprising a polyalkylene glycol urethane-modified poly (meth) acrylate obtained by reacting with a urethanization catalyst, a polyisocyanate compound, and a second reaction raw material containing a compound containing a (meth) acryloyl group and a hydroxyl group. It contains urethane-modified poly (meth) acrylate obtained by reacting with use.

In the first invention, the coating composition of the second invention contains a polyol compound other than polyalkylene glycol in the first reaction raw material or the second raw material.
In the coating composition of the third invention, in the first or second invention, the polyisocyanate compound has a cyclic skeleton, the number of isocyanate groups is 2 to 6, and a (meth) acryloyl group and a hydroxyl group. The compound to be contained has a pentaerythritol skeleton, and the number of (meth) acryloyl groups is 1 to 3.

  In the coating composition of the fourth invention, in any one of the first to third inventions, the ratio of the polyalkylene glycol residue in the coating composition is 20 to 85% by mass, and the ratio of urethane bonds is 3. -30 mass%, and the ratio of a (meth) acryloyl group is 0.1-30 mass%.

The coating of the fifth invention is obtained by curing the coating composition of any one of the first to fourth inventions by a curing means.
The antifogging sheet of the sixth invention is characterized in that the covering of the fifth invention is provided on one surface of the synthetic resin film and the pressure-sensitive adhesive layer is provided on the other surface.

According to the present invention, the following effects can be exhibited.
The coating composition of the first invention contains polyalkylene glycol urethane-modified poly (meth) acrylate and urethane-modified poly (meth) acrylate. For this reason, when the coating composition is coated on the coating object, the urethane-modified poly (meth) acrylate is oriented toward the coating object side, and the polyalkylene glycol urethane-modified poly (meth) acrylate is oriented toward the surface side. It is estimated to be. When the coating composition is cured in this state, adhesion performance is expressed on the object to be coated, anti-fogging performance is expressed on the surface, and water resistance, weather resistance and scratch resistance are based on the crosslinked structure. Is presumed to be exhibited.

  Therefore, based on the coating composition, a coating capable of exhibiting a good balance of antifogging performance, water resistance performance, adhesion performance, weather resistance performance and scratch resistance performance can be obtained. Therefore, according to the coating composition, it is possible to obtain a coating having high practical value performance that cannot be obtained by the conventional coating composition on the surface of the coating object such as synthetic resin, inorganic glass, metal and the like. .

  In the coating composition of the second invention, since the polyol compound is contained in the first reaction raw material or the second reaction raw material, the reactivity with the polyisocyanate compound is enhanced, and at the same time, based on the hydroxyl group (hydroxyl group). The effect can be demonstrated. Therefore, in addition to the effects of the first invention, a coating that is superior in terms of water resistance and adhesion performance can be obtained.

  In the coating composition of the third invention, the polyisocyanate compound has a cyclic skeleton, the number of isocyanate groups is 2 to 6, the compound containing a (meth) acryloyl group and a hydroxyl group has a pentaerythritol skeleton, And the (meth) acryloyl group number is 1-3. For this reason, the crosslink density of the coating can be improved, and in addition to the effects of the first or second invention, the coating is more excellent in terms of antifogging performance, scratch resistance, adhesion performance, and water resistance. Can be obtained.

  In the coating composition of the fourth invention, the proportion of polyalkylene glycol residues is 20 to 85 mass%, the proportion of urethane bonds is 3 to 30 mass%, and the proportion of (meth) acryloyl groups is 0.1 to 30 mass%. %. Therefore, in addition to the effects of any one of the first to third inventions, the antifogging performance, the scratch resistance performance, the adhesion performance, and the water resistance performance can be expressed in a well-balanced manner.

  The coating of the fifth invention is obtained by curing the coating composition of any one of the first to third inventions by a curing means such as irradiation with active energy rays or heating. For this reason, the coating can be easily formed on the surface of the coating object, and the coating object can have an excellent anti-fogging function.

  According to the antifogging sheet of the sixth invention, the covering of the fifth invention is provided on one surface of the synthetic resin film, and the pressure-sensitive adhesive layer is provided on the other surface. Therefore, the effect of the covering of the fifth invention can be exhibited on one surface of the synthetic resin film, and the other surface can be easily attached to the covering object via the pressure-sensitive adhesive layer.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The coating composition of this embodiment contains polyalkylene glycol urethane-modified poly (meth) acrylate and urethane-modified poly (meth) acrylate. In addition, (meth) acrylate means both acrylate and methacrylate. A polyalkylene glycol urethane-modified poly (meth) acrylate is obtained by reacting a first reaction raw material containing a polyisocyanate compound, a polyalkylene glycol, and a compound containing a (meth) acryloyl group and a hydroxyl group using a urethanization catalyst. It is done. Here, the polyisocyanate compound means a compound having a plurality of isocyanate groups. The urethane-modified poly (meth) acrylate is obtained by reacting a second reaction raw material containing a polyisocyanate compound and a compound containing a (meth) acryloyl group and a hydroxyl group using a urethanization catalyst. A coating is formed by curing the coating composition by a curing means.

  First, polyalkylene glycol urethane-modified poly (meth) acrylate will be described. The mass (weight) average molecular weight of the polyalkylene glycol urethane-modified poly (meth) acrylate is usually 500 to 100,000, preferably 500 to 50,000, and more preferably 500 to 30,000. When the mass average molecular weight is less than 500, it is difficult to synthesize polyalkylene glycol urethane-modified poly (meth) acrylate, which is not practical. On the other hand, when the mass average molecular weight exceeds 100,000, the polyalkylene glycol urethane-modified poly (meth) acrylate has a high viscosity, and the coating property of the coating composition tends to be lowered.

  The proportion of the polyalkylene glycol residue in the polyalkylene glycol urethane-modified poly (meth) acrylate is preferably 20 to 90% by mass, and more preferably 50 to 80% by mass. When this ratio is less than 20% by mass, the resulting coating has insufficient antifogging performance, and when it exceeds 90% by mass, the strength, scratch resistance, etc. of the coating tend to decrease.

  The number of (meth) acryloyl groups in the polyalkylene glycol urethane-modified poly (meth) acrylate is preferably 3-20, more preferably 5-15. When the (meth) acryloyl group number is less than 3, the coating film strength and water resistance performance of the coating (coating film) decrease, and when it exceeds 20, the antifogging performance of the coating tends to decrease.

  As a method for synthesizing polyalkylene glycol urethane-modified poly (meth) acrylate, a generally known method for producing urethane acrylate is adopted, and typical examples thereof are shown below, but are not limited thereto. Moreover, when handling a polymeric compound at high temperature at the time of manufacture, polymerization inhibitors, such as 2, 6-di-t-butyl- p-cresol, can also be added as needed.

  Then, the manufacturing method of polyalkylene glycol urethane modified poly (meth) acrylate is demonstrated. One of the production methods is to first react a polyalkylene glycol and a polyisocyanate compound in the presence of a urethanization catalyst to form a urethane oligomer having an isocyanate group at the terminal. Thereafter, a polyol compound and a compound containing a (meth) acryloyl group and a hydroxyl group are reacted in this order to form a polyalkylene glycol urethane-modified poly (meth) acrylate having a (meth) acryloyl group at the terminal.

As specific examples thereof, as shown in the following chemical formula (1), first, polyalkylene glycol (R ¹ (OH) ₂ , n mol, where R ¹ is a residue of polyalkylene glycol excluding a hydroxyl group) and A diisocyanate compound (R ² (NCO) ₂ , n + 1 mol, where R ² is a residue of a diisocyanate compound excluding an isocyanate group) as a polyisocyanate compound, and dibutyltin dilaurate ([CH ₃ (CH ₂ ) ₃ as a catalyst) ] ₂ Sn [OCO (CH _{2) 10} CH _{3] 2)} is added. When it is reacted by heating to 40 to 120 ° C., a urethane oligomer having isocyanate groups (—NCO) at both ends is obtained.

ここで、Ｕはウレタン結合（−ＮＨＣＯＯ−）を示す。

Here, U represents a urethane bond (—NHCOO—).

To this urethane oligomer (3 mol), a triol compound (R ³ (OH) ₃ , 1 mol, where R ³ is a residue of a triol compound excluding a hydroxyl group) as a polyol compound was added in a dibutyltin dilaurate residue of 40 to 40%. By making it react at 120 degreeC, the urethane oligomer like following Chemical formula (2) is formed.

このウレタンオリゴマー（１モル）にジブチルスズジラウレートの残存下で（メタ）アクリロイル基及びヒドロキシル基を含有する化合物（ＣＨ₂＝ＣＨＣＯＯＲ⁴ＯＨ、３モル、ここでＲ⁴は（メタ）アクリロイル基を除いた化合物の残基である）を４０〜１２０℃で反応させる。すると、下記化学式（３）のように末端のイソシアネート基に（メタ）アクリロイル基及びヒドロキシル基を含有する化合物のヒドロキシル基が付加し、末端に（メタ）アクリロイル基を有するポリアルキレングリコールウレタン変性ポリ（メタ）アクリレートが得られる。

A compound containing (meth) acryloyl group and hydroxyl group in the presence of dibutyltin dilaurate in this urethane oligomer (1 mol) (CH ₂ ═CHCOOR ⁴ OH, 3 mol, where R ⁴ excludes (meth) acryloyl group) Compound residue) is reacted at 40-120 ° C. Then, as shown in the following chemical formula (3), a hydroxyl group of a compound containing a (meth) acryloyl group and a hydroxyl group is added to the isocyanate group at the terminal, and the polyalkylene glycol urethane-modified poly (poly (ethylene)) having a (meth) acryloyl group at the terminal is added. A (meth) acrylate is obtained.

ここでＲ⁵は−Ｒ⁴−ＯＣＯ−ＣＨ＝ＣＨ₂を示す。

Here, R ⁵ represents —R ⁴ —OCO—CH═CH ₂ .

  In another production method, first, a polyisocyanate compound and a compound containing a (meth) acryloyl group and a hydroxyl group are reacted in the presence of a urethanization catalyst to obtain a compound having two or more isocyanate groups. Thereafter, polyalkylene glycol is reacted to form a urethane oligomer having isocyanate groups at both ends. This is further reacted with a compound containing a (meth) acryloyl group and a hydroxyl group to form a polyalkylene glycol urethane-modified poly (meth) acrylate.

As a specific example, as shown in the following chemical formula (4), as a polyisocyanate compound, for example, a triisocyanate compound (R ⁶ (NCO) ₃ , 1 mol, where R ⁶ is a triisocyanate compound excluding an isocyanate group) And a compound (1 mol) containing a (meth) acryloyl group and a hydroxyl group is heated to 40 to 120 ° C. in the presence of dibutyltin dilaurate to synthesize a diisocyanate compound.

このジイソシアネート化合物（ｎ＋１モル）及びポリアルキレングリコール（ｎモル）をジブチルスズジラウレート残存下で４０〜１２０℃にて反応させて、下記化学式（５）のようなイソシアネート基を両末端に有するウレタンオリゴマーを形成する。

This diisocyanate compound (n + 1 mol) and polyalkylene glycol (n mol) are reacted at 40 to 120 ° C. with dibutyltin dilaurate remaining to form a urethane oligomer having isocyanate groups at both ends as shown in the following chemical formula (5). To do.

このウレタンオリゴマー（１モル）に（メタ）アクリロイル基及びヒドロキシル基を含有する化合物（２モル）を４０〜１２０℃で反応させると、下記化学式（６）に示すように末端のイソシアネート基に（メタ）アクリロイル基及びヒドロキシル基を含有する化合物のヒドロキシル基が付加する。そして、末端に（メタ）アクリロイル基を有するポリアルキレングリコールウレタン変性ポリ（メタ）アクリレートが得られる。

When this urethane oligomer (1 mol) is reacted with a compound (2 mol) containing a (meth) acryloyl group and a hydroxyl group at 40 to 120 ° C., as shown in the following chemical formula (6), ( ) The hydroxyl group of a compound containing an acryloyl group and a hydroxyl group is added. And the polyalkylene glycol urethane modified poly (meth) acrylate which has a (meth) acryloyl group at the terminal is obtained.

更に他の製造方法は、まずポリイソシアネート化合物及びポリアルキレングリコールをウレタン化触媒の存在下に反応させてイソシアネート基を両末端に有する化合物を得る。その後、（メタ）アクリロイル基及びヒドロキシル基を含有する化合物をイソシアネート基と反応させてポリアルキレングリコールウレタン変性ポリ（メタ）アクリレートを形成する。

In still another production method, a polyisocyanate compound and polyalkylene glycol are first reacted in the presence of a urethanization catalyst to obtain a compound having isocyanate groups at both ends. Thereafter, a compound containing a (meth) acryloyl group and a hydroxyl group is reacted with an isocyanate group to form a polyalkylene glycol urethane-modified poly (meth) acrylate.

  As a specific example, as shown in the following chemical formula (7), first, for example, a diisocyanate compound (n + 1 mol) and a polyalkylene glycol (n mol) are reacted as polyisocyanate compounds at 40 to 120 ° C. in the presence of dibutyltin dilaurate. . Thus, a diisocyanate compound having an isocyanate group at both ends as shown in the following chemical formula (7) is synthesized.

このジイソシアネート化合物（１モル）に（メタ）アクリロイル基及びヒドロキシル基を含有する化合物（２モル）をジブチルスズジラウレート残存下４０〜１２０℃で反応させると、下記化学式（８）のようにイソシアネート基に（メタ）アクリロイル基及びヒドロキシル基を含有する化合物のヒドロキシル基が付加する。そして、両末端に（メタ）アクリロイル基を有するポリアルキレングリコールウレタン変性ポリ（メタ）アクリレートを形成する。

When this diisocyanate compound (1 mol) is reacted with a compound (2 mol) containing a (meth) acryloyl group and a hydroxyl group at 40 to 120 ° C. with dibutyltin dilaurate remaining, an isocyanate group ( A hydroxyl group of a compound containing a (meth) acryloyl group and a hydroxyl group is added. Then, a polyalkylene glycol urethane-modified poly (meth) acrylate having (meth) acryloyl groups at both ends is formed.

上記に用いられる第１反応原料について以下に説明するが、使用可能な化合物は例示される化合物に限られるものではない。

Although the 1st reaction raw material used for the above is demonstrated below, the compound which can be used is not restricted to the illustrated compound.

  Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 2,6-isophorone diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, cyclohexyl isocyanate, trimethylhexamethylene diisocyanate, cyclohexane- 1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, diisocyanate compounds such as 1,5-naphthalene diisocyanate, trimer isocyanurates of the above diisocyanates, and 1 mol of triol compounds such as trimethylolpropane Triisocyanate compounds such as adducts with 3 mol of the above diisocyanate compounds, pentaerythrito Tetraol compound 1 mol of the diisocyanate compound 4 adduct tetra isocyanate compound with molar such as Le, isocyanurate type, biuret type, and polyisocyanurate compound of adduct type and the like.

  Among these, from the viewpoint of improving the scratch resistance performance of the coating, 1 mole of a triol compound such as trimethylolpropane and 3 moles of the above diisocyanate compound and 1 mole of a tetraisole compound such as pentaerythritol and the like. Preferred are polyisocyanurate compounds such as tetraisocyanate compounds, isocyanurate type, burette type, and adduct type adducts with 4 moles of the above-mentioned diisocyanate compounds. And compounds having 2 to 6 isocyanate groups are particularly preferred.

  As the polyalkylene glycol, polyethylene glycol is most preferable from the viewpoint of anti-fogging performance of the coating, and a copolymer of ethylene glycol and propylene glycol is also preferable. In the case of a copolymer of ethylene glycol and propylene glycol, by increasing the proportion of ethylene glycol, hydrophilicity can be increased and antifogging performance can be improved. The mass average molecular weight of the polyalkylene glycol is preferably 100 to 80,000, and more preferably 100 to 30000. When the mass average molecular weight is less than 100, the antifogging performance of the coating is insufficient, and when it exceeds 80000, the viscosity becomes high and the workability in coating the coating composition is deteriorated. In the case of polyethylene glycol, the mass average molecular weight is preferably 100 to 10,000, and more preferably 200 to 3000. When the mass average molecular weight is less than 100, the antifogging performance of the coating is insufficient, and when it exceeds 10,000, the crystallinity of the polyethylene glycol chain is increased and the coating property is lowered.

  In the coating composition, a polyol compound other than the polyalkylene glycol described above can be blended. Here, the polyol compound refers to a compound having a plurality of hydroxyl groups (hydroxyl groups). Examples of such a polyol compound include diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polypropylene glycol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, and 2-methyl-1,3. -Butanediol, neopentyl glycol, 2-menthylpentanediol, 3-methylpentanediol, 2,2,4-trimethyl-1,6-hexanediol, 3,3,5-trimethyl-1,6-hexanediol, Diols such as 2,3,5-trimethylpentanediol and 1,6-hexanediol, first aliphatic triols such as trimethylolpropane and trimethylolethane, glycerin, tri (2-hydroxyethyl) isocyanurate, pen Primary aliphatic tetraol of erythritol include ditrimethylolpropane like.

  The compound containing a (meth) acryloyl group and a hydroxyl group includes all compounds having a (meth) acryloyl group and a hydroxyl group. Examples include (meth) acrylic acid esters containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; (meth) acrylic such as pyrocaprolactone-modified (meth) acrylic acid esters The compound obtained by reaction of an acid and a polyol compound is mentioned.

  Among these, from the viewpoint of improving the water resistance performance and adhesion performance of the coating, a compound obtained by a reaction of (meth) acrylic acid and a polyol compound is preferable, and a compound containing a (meth) acryloyl group and a hydroxyl group is pentane. A compound having an erythritol skeleton and having 1 to 3 (meth) acryloyl functional groups, such as pentaerythritol tri (meth) acrylate, is particularly preferable. Therefore, it is preferable to use such a compound containing a (meth) acryloyl group and a hydroxyl group in combination with a compound having a cyclic skeleton and having 2 to 6 isocyanate groups as the polyisocyanate compound. In this case, it is preferable to employ the above-described configuration for both the polyalkylene glycol urethane-modified poly (meth) acrylate and the urethane-modified poly (meth) acrylate, but the above-described configuration can also be employed for either one.

  Examples of the urethanization catalyst include triethylenediamine, morpholine, N-ethylmorpholine, piperidine, triethanolamine, triethylamine, dibutyltin dilaurate, stannous oleate, dibutyltin oxide and the like.

  The content of the polyalkylene glycol urethane-modified poly (meth) acrylate contained in the coating composition is preferably 10 to 95% by mass, more preferably 20 to 80% by mass in the coating composition. When the content is less than 10% by mass, the antifogging performance of the coating formed from the coating composition is insufficient, and when it exceeds 95% by mass, the scratch resistance and adhesion performance of the coating are insufficient. .

  In the production methods shown in the chemical formulas (1) to (6), since the number of (meth) acryloyl groups is increased, the crosslinking density can be increased by increasing the crosslinking points, and the water resistance performance, scratch resistance performance, etc. of the coating can be improved. Can be improved. On the other hand, in the production methods shown in the chemical formulas (7) and (8), a coating composition having a relatively low molecular weight can be obtained, and the viscosity can be lowered to improve the coating property.

  Next, the urethane-modified poly (meth) acrylate will be described. The mass average molecular weight is usually 350 to 100,000, preferably 500 to 50,000, and more preferably 500 to 30,000. When the mass average molecular weight is less than 350, the production is difficult, and when it exceeds 100,000, the viscosity becomes high and the coatability tends to be lowered.

  The (meth) acryloyl group preferably has 3 to 20 functional groups, more preferably 6 to 15 functional groups. If it is less than trifunctional, the strength, water resistance and adhesion performance of the coating will decrease, and if it exceeds 20 functionality, the antifogging performance of the coating will be insufficient.

  As a method for producing a urethane-modified poly (meth) acrylate, a generally known method for producing a urethane (meth) acrylate is adopted, and typical examples thereof are shown below, but are not limited thereto. Moreover, when handling a polymeric compound at high temperature at the time of manufacture, polymerization inhibitors, such as 2, 6-di-t-butyl- p-cresol, can also be added as needed.

  In one production method, a polyisocyanate compound and a polyol compound are first reacted in the presence of a urethanization catalyst to form a urethane oligomer having an isocyanate group at the terminal. Thereafter, a compound containing a (meth) acryloyl group and a hydroxyl group is reacted to form a urethane-modified poly (meth) acrylate having a (meth) acryloyl group at the terminal.

  As a specific example thereof, as shown in the following chemical formula (9), first, a diisocyanate compound (3 mol) as a polyisocyanate compound and a triol (1 mol) as a polyol compound, and 40 to 120 ° C. in the presence of dibutyl sujidilaurate as a catalyst. To react. Thereby, the urethane oligomer which has an isocyanate group (-NCO) at the terminal like following Chemical formula (9) is obtained.

このウレタンオリゴマー（１モル）にジブチルスズジラウレート残存下で（メタ）アクリロイル基及びヒドロキシル基を含有する化合物（３モル）を４０〜１２０℃で反応させる。これにより、下記化学式（１０）に示すようにイソシアネート基に（メタ）アクリロイル基及びヒドロキシル基を含有する化合物のヒドロキシル基が付加し、末端に（メタ）アクリロイル基を有するウレタン変性ポリ（メタ）アクリレートが得られる。

This urethane oligomer (1 mol) is reacted with a compound (3 mol) containing a (meth) acryloyl group and a hydroxyl group at 40 to 120 ° C. with dibutyltin dilaurate remaining. Thereby, as shown in the following chemical formula (10), the hydroxyl group of the compound containing a (meth) acryloyl group and a hydroxyl group is added to the isocyanate group, and the urethane-modified poly (meth) acrylate having a (meth) acryloyl group at the terminal. Is obtained.

また他の製造方法は、まずポリイソシアネート化合物と（メタ）アクリロイル基及びヒドロキシル基を含有する化合物とをウレタン化触媒の存在下に反応させて２個以上のイソシアネート基を有する化合物を得た後、ポリオール化合物と反応させてイソシアネート基を末端に有するウレタンオリゴマーを形成する。これに（メタ）アクリロイル基及びヒドロキシル基を含有する化合物を更に反応させることにより、ウレタン変性ポリ（メタ）アクリレートが得られる。

In another production method, after a polyisocyanate compound and a compound containing a (meth) acryloyl group and a hydroxyl group are reacted in the presence of a urethanization catalyst to obtain a compound having two or more isocyanate groups, A urethane oligomer having an isocyanate group at the terminal is formed by reacting with a polyol compound. A urethane-modified poly (meth) acrylate is obtained by further reacting this with a compound containing a (meth) acryloyl group and a hydroxyl group.

  As a specific example, as shown in the following chemical formula (11), a triisocyanate compound (1 mol) as a polyisocyanate compound and a compound (1 mol) containing a (meth) acryloyl group and a hydroxyl group are first converted into dibutyltin dilaurate. To produce a diisocyanate compound by heating to 40 to 120 ° C. and reacting.

このジイソシアネート化合物（ｎ＋１モル）とポリオール化合物としてジオール化合物（ｎモル）とをジブチルスズジラウレートの残存下４０〜１２０℃にて反応させ、下記化学式（１２）に示すようなイソシアネート基を両末端に有するウレタンオリゴマーを形成する。

This diisocyanate compound (n + 1 mol) and a diol compound (n mol) as a polyol compound are reacted at 40 to 120 ° C. in the presence of dibutyltin dilaurate, and a urethane having isocyanate groups as shown in the following chemical formula (12) at both ends. Form oligomers.

このウレタンオリゴマー（１モル）に（メタ）アクリロイル基及びヒドロキシル基を含有する化合物（２モル）をジブチルスズジラウレート残存下４０〜１２０℃で反応させると、下記化学式（１３）に示すように末端のイソシアネート基に（メタ）アクリロイル基及びヒドロキシル基を含有する化合物のヒドロキシル基が付加する。これにより、末端に（メタ）アクリロイル基を有するウレタン変性ポリ（メタ）アクリレートが得られる。

When this urethane oligomer (1 mol) is reacted with a compound (2 mol) containing a (meth) acryloyl group and a hydroxyl group at 40 to 120 ° C. with dibutyltin dilaurate remaining, the terminal isocyanate is represented by the following chemical formula (13). A hydroxyl group of a compound containing a (meth) acryloyl group and a hydroxyl group is added to the group. Thereby, the urethane-modified poly (meth) acrylate having a (meth) acryloyl group at the terminal is obtained.

更に他の製造方法は、ポリイソシアネート化合物と（メタ）アクリロイル基及びヒドロキシル基を含有する化合物とをウレタン化触媒の存在下に反応させてウレタン変性ポリ（メタ）アクリレートを形成する方法である。

Yet another production method is a method of forming a urethane-modified poly (meth) acrylate by reacting a polyisocyanate compound with a compound containing a (meth) acryloyl group and a hydroxyl group in the presence of a urethanization catalyst.

  As a specific example thereof, as shown in the following chemical formula (14), a diisocyanate compound (1 mol) and a compound (2 mol) containing a (meth) acryloyl group and a hydroxyl group are first used as a polyisocyanate compound in the presence of dibutyltin dilaurate. When the reaction is carried out at 40 to 120 ° C., the hydroxyl group of the compound containing a (meth) acryloyl group and a hydroxyl group is added to the isocyanate group as shown in the following chemical formula (14). As a result, urethane-modified poly (meth) acrylate having (meth) acryloyl groups at both ends is obtained.

上記に用いられる第２反応原料について以下に説明するが、使用可能な化合物は例示された化合物に限られるものではない。第２反応原料であるポリイソシアネート化合物、（メタ）アクリロイル基及びヒドロキシル基を含有する化合物、ポリオール化合物、ウレタン化触媒は、ポリアルキレングリコールウレタン変性ポリ（メタ）アクリレートに例示されている化合物を例として挙げることができる。

Although the 2nd reaction raw material used above is demonstrated below, the compound which can be used is not restricted to the illustrated compound. The polyisocyanate compound, the (meth) acryloyl group and the hydroxyl group-containing compound, the polyol compound, and the urethanization catalyst that are the second reaction raw materials are exemplified by the compounds exemplified in the polyalkylene glycol urethane-modified poly (meth) acrylate. Can be mentioned.

  In the production methods shown in the chemical formulas (9) to (13), since the number of (meth) acryloyl groups is increased, the crosslinking density can be increased by increasing the number of crosslinking points, and the water resistance performance, scratch resistance performance, etc. of the coating can be improved. Can be improved. On the other hand, in the production method shown in the chemical formula (14), a coating composition having a relatively low molecular weight can be obtained, the viscosity of the coating composition can be lowered, and the coating property can be improved.

  The content of the urethane-modified poly (meth) acrylate contained in the coating composition is preferably 5 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 20 to 40% in the coating composition. is there. When the content is less than 5% by mass, the strength, scratch resistance and adhesion performance of the coating formed from the coating composition are insufficient, and when it exceeds 90% by mass, the antifogging performance of the coating is achieved. Decreases.

  In the coating composition, the polyalkylene glycol urethane is modified so that the polyalkylene glycol residue is 20 to 85% by mass, the urethane bond is 3 to 30% by mass, and the (meth) acryloyl group is 0.1 to 30% by mass. It is preferable to adjust the blending ratio of poly (meth) acrylate and urethane-modified poly (meth) acrylate. The coating composition can mainly improve anti-fogging performance by increasing the content of polyalkylene glycol urethane-modified poly (meth) acrylate, and increase the content of urethane-modified poly (meth) acrylate. Can mainly improve water resistance, adhesion performance, weather resistance and scratch resistance.

  When the polyalkylene glycol residue in the coating composition is less than 20% by mass, the antifogging performance of the coating is insufficient, and when it exceeds 85% by mass, the scratch resistance and adhesion performance of the coating are deteriorated. When the urethane bond is less than 3% by mass, the scratch resistance performance of the coating is lowered, and when it exceeds 30% by mass, the antifogging performance of the coating is lowered. Further, when the (meth) acryloyl group is less than 0.1% by mass, the water resistance of the coating is lowered, and when it exceeds 30% by mass, the antifogging performance of the coating tends to be lowered.

  The coating composition containing the above compound can be cured by irradiation with active energy rays or heating as a curing means. For example, when the active energy ray is ultraviolet light, the irradiation with ultraviolet light generates radicals to initiate polymerization of the (meth) acryloyl group. In this case, it is necessary to add a photopolymerization initiator for initiating polymerization of the (meth) acryloyl group. However, it is not particularly necessary for curing with an active energy ray other than ultraviolet rays, such as an electron beam or cobalt γ ray.

  Specific examples of the photopolymerization initiator include benzoin or benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, aromatic ketones such as benzophenone, benzoylbenzoic acid, and methyl-2-benzoylbenzoate. , Α-dicarbonyls such as benzyl, benzyl ketals such as benzyldimethyl ketal and benzyl diethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy Cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, 1- [ 4- (2-Hi Acetophenones such as loxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 2- Anthraquinones such as methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, thioxanthones such as 2,4-dimethylthioxanthone, 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, 1-phenyl-1,2- Α-acyloximes such as propanedione-2- (o-ethoxycarbonyl) oxime, amines such as ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 3,3 ′, 4,4′- Tetra- (t-butylperoxycarbonyl) benzophenone, etc. Peroxide bond-containing compounds and the like are used.

  Among these, acetophenones such as 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and fragrances such as benzophenone and methyl-2-benzoylbenzoate It is easy to handle peroxide-containing compounds such as aromatic ketones, benzyl ketals such as benzyl dimethyl ketal, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, and the ability to initiate polymerization It is particularly preferable because of high.

  The content of the photopolymerization initiator in the coating composition is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the coating composition. When the content is less than 0.01 parts by mass, the coating composition is insufficiently cured, and when it exceeds 20 parts by mass, the performance of the coating tends to be impaired.

  In addition, the coating composition contains polyethylene glycol poly (meth) acrylate, (meth) acrylate containing a hydroxyl group, (meth) acrylate containing an amide group, etc. in order to improve the antifogging performance of the coating. Etc. may be added. In addition, monofunctional or polyfunctional monomers other than those mentioned above and polymers thereof, surfactants, ultraviolet absorbers, light stabilizers, leveling agents, storage, etc. You may add a stabilizer, a heat stabilizer, a sensitizer, a hardening | curing agent, an inorganic filler, etc. Moreover, in order to improve adhesion | attachment performance with a base material, you may add the silane coupling agent used normally, a titanate coupling agent, etc. Furthermore, in order to cure the coating composition by heating, a thermal polymerization initiator such as benzoyl peroxide may be added.

  Examples of the polyethylene glycol poly (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol # 200 di (meth) acrylate (in the compound name) # 200 indicates that the mass average molecular weight of the polyethylene glycol difference portion in the molecule is 200, and the same applies to #arabic numerals described below) polyethylene glycol # 400 di (meth) acrylate, polyethylene glycol # 600 di (meta ) Acrylate, polyethylene glycol # 1000 di (meth) acrylate, polyethylene glycol # 2000 di (meth) acrylate, polyethylene glycol # 3000 di (meth) acrylate, Triethylene glycol # 4000 di (meth) acrylate, polyethylene glycol tri (meth) acrylate.

  Examples of the (meth) acrylate containing a hydroxyl group include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2- (meth) acryloyloxyethyl phthalate. , Di (meth) acrylated isocyanurate, epichlorohydridone modified allyl (meth) acrylate, epichlorohydridone modified 1,6-hexanediol di (meth) acrylate, epichlorohydridone modified propylene glycol di (meth) acrylate, (poly) propylene glycol Diglycidyl ether (meth) acrylate, hexahydrophthalic acid diglycidyl ester (meth) acrylate, bis (2-hydroxy-3- (1-oxo-2-propenyl)) phthalate ) Propyl ester (meth) acrylate, bisphenol A-modified glycidyl ether (meth) acrylate, 1,6-hexanediol diglycidyl ether (meth) acrylate, glycerin polyglycidyl ether (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( And (meth) acrylate and allyl alcohol glycidyl ether (meth) acrylate.

  Examples of (meth) acrylates containing amide groups include (meth) acrylamide, methyl (meth) acrylamide, dimethyl (meth) acrylamide, ethyl (meth) acrylamide, diethyl (meth) acrylamide, propyl (meth) acrylamide, and dipropyl ( Examples include meth) acrylamide, methylethyl (meth) acrylamide, butyl (meth) acrylamide, dibutyl (meth) acrylamide, and diisobutyl (meth) acrylamide.

  Examples of monofunctional or polyfunctional monomers and polymers thereof include 1,4-butanediol mono (meth) acrylate, glycerol (meth) acrylate, caprolactone-modified (meth) acrylate, polyethylene glycol mono (meth) acrylate, Polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol block copolymer mono (meth) acrylate, ethylene oxide-modified phthalic acid monoacrylate, ethylene oxide-propylene oxide-modified mono (meth) acrylate, epichlorohydrin-modified ethylene glycol Di (meth) acrylate, 3-chloro-2-hydroxypropyl methacrylate, 2-hydroxy-3-methacryloxypropyltrimethylan Nitric chloride, ethylene oxide modified phosphoric acid mono (meth) acrylate, ethylene oxide modified phenoxylated phosphoric acid mono (meth) acrylate, ethylene oxide modified octoxylated phosphoric acid mono (meth) acrylate ester, alkoxy modified phosphoric acid mono (meth) acrylate Esters, ethylene oxide modified succinic acid mono (meth) acrylate, triglycerol diacrylate, glycerol monoacrylate monomethacrylate, glycerol dimethacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, epichlorohydrin modified glycerol triacrylate , Epichlorohydrin modified 1,6-hexanediol diacrylate, epichlorohydrin Propylene glycol diacrylate, epichlorohydrin-modified trimethylolpropane triacrylate, epichlorohydrin-modified phthalic acid diacrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, ethylene oxide henseiphosphoric acid tri (meth) acrylate, butanecarboxylic acid di {(meta ) Acryloyloxyethyl} ester and the like.

  As the surfactant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or the like that is generally used is selected and used. Specifically, nonionic surfactants include polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol, polyoxyethylene nonylphenol. Polyoxyethylene alkyl aryl ethers such as polyoxyethylene acylesters such as polyoxyethylene glycol monostearate, polyoxyethylene acylesters such as polypropylene glycol ethylene oxide adducts, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, etc. Phosphoric acid of ethylene sorbitan aliphatic esters, alkyl phosphate esters, polyoxyethylene alkyl ether phosphate esters Ester ethers, sugar esters, and cellulose ethers and the like.

  Examples of anionic surfactants include fatty acid salts such as sodium oleate and potassium oleate, higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfones such as sodium dodecylbenzenesulfonate and sodium alkylnaphthalenesulfonate. Examples include acid salts and alkylnaphthalene sulfonates, naphthalene sulfonic acid formalin condensates, dialkyl sulfosuccinates, dialkyl phosphate salts, polyoxyethylene sulfate salts such as sodium polyoxyethylene alkylphenyl ether sulfate, and the like.

  Cationic surfactants include ethanolamines, laurylamine acetate, triethanolamine monoformate, amine salts such as stearamide ethyl diethylamine acetate, lauryltrimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium And quaternary ammonium salts such as chloride and lauryldimethylbenzylammonium chloride.

  Examples of the zwitterionic surfactant include fatty acid type amphoteric surfactants such as dimethylalkyl lauryl betaine and dimethylalkyl stearyl betaine, sulfonic acid type amphoteric surfactants such as dimethylalkyl sulfobetaine, and alkylglycine.

  Examples of UV absorbers include benzophenone UV absorbers such as 2,4-hydroxybenzophenone, benzotriazole UV absorbers such as 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, Benzoate ultraviolet absorbers such as 4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, salicylate ultraviolet absorbers such as pt-butylphenyl salicylate, ethyl-cyano- And cyanoacrylate-based ultraviolet absorbers such as 3,3-diphenyl acrylate.

  Examples of the light stabilizer include hindered amine light stabilizers such as bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacin. Examples of the leveling agent include silicon-based leveling agents such as polyether-modified polydimethylsiloxane, acrylic leveling agents, and the like.

  Moreover, a coating composition becomes a comparatively low-viscosity liquid by selecting suitably the kind of compounding component, and addition amount. In that case, coating is possible without adding a solvent. This is very advantageous because it does not require a solvent drying step in the processing line. In any case where the viscosity of the coating composition is high and the viscosity is relatively low, a solvent may be added for the purpose of adjusting the film thickness and improving the mirror surface. Solvents used here include alcohols such as ethanol, isopropanol, n-butanol, isobutanol and methoxyethoxybutanol, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, glycols such as polyethylene glycol monomethyl alcohol and polypropylene glycol And ketones such as acetone, dimethyl ketone, dipropyl ketone, and methyl ethyl ketone are preferred.

  Next, the coating based on the above coating composition will be described. As described above, this coating is obtained by curing the coating composition by a curing means. The coating composition is usually coated (coated) on a coating object (base material) to form a coating. The film thickness of the coating composition on the object to be coated may be any film thickness that can be cured by irradiation with active energy rays or heating as a curing means, preferably 0.1 to 1000 μm, more preferably 1 to 500 μm. It is. When the film thickness is less than 0.1 μm, it is not easy to form such a thin film thickness, and when it exceeds 1000 μm, uniform curing tends to be difficult.

  As the covering object, a plate material such as synthetic resin, inorganic glass, transparent ceramic, metal, mirror surface material, sheet material, film or the like is used. The synthetic resin is preferably a synthetic resin having good heat resistance such as polyester, such as polycarbonate, polyamide, polyimide, polystyrene, polypropylene, polyethylene terephthalate, triacetyl cellulose, acrylic resin, acrylonitrile-butadiene-styrene copolymer resin. Examples of the metal include aluminum and stainless steel. The thickness of the object to be coated may be any thickness, but 1 μm to 20 cm is preferable because it can be easily molded.

  As a coating method, any method according to a conventional method such as a gravure method, a roll coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method, a knife coating method, a die coating method, or a spin coating method may be used. . When coating, if necessary, a pretreatment such as corona discharge or primer coating may be applied to the substrate in advance in order to improve the adhesion between the coating target and the coating (coating).

As the curing means, means such as irradiation with active energy rays and heating are used. As active energy rays, radiation, ultraviolet rays and visible rays can be used. In the case of radiation irradiation, α rays, β rays, γ rays and electron rays can be used. In view of this adverse effect, it is preferable to use an electron beam accelerator with low energy and high output. The dose is preferably in the range of 0.1-20 Mrad, particularly preferably in the range of 0.5-5 Mrad. When irradiating ultraviolet rays or visible rays, the wavelength is not particularly limited as long as the polymerization initiator used can absorb, but the wavelength is preferably 200 to 800 nm, more preferably 300 to 600 nm. The irradiation amount of ultraviolet rays and visible rays is preferably 10 mJ / cm ^{2 to 5} J / cm ² . As the light source, a high-pressure mercury lamp, a low-pressure mercury lamp, a halogen lamp, a xenon lamp, an excimer laser, a dye laser, a YAG laser, sunlight, or the like can be used.

  When irradiating with ultraviolet rays or visible rays, the reaction may be carried out in the air, or in an inert gas atmosphere or in a state covered with a transparent resin film, a glass plate, etc. in order to reduce curing inhibition by oxygen Irradiation may be performed with

  In addition, a thermal polymerization initiator is added during heating. Such thermal polymerization initiators include all known chemical substances that generate radicals upon heating. For example, a peroxide bond-containing compound such as benzoyl peroxide, lauryl peroxide, t-butylperoxy-1-ethylhexanoate, t-butylperoxyneodecanoate, a redox agent such as potassium persulfate, Examples include azo compounds. The heating temperature is preferably in the range of 60 to 200 ° C.

  Next, the anti-fogging sheet is configured by providing the covering on one surface of a synthetic resin film and providing an adhesive layer on the other surface. Here, the sheet includes the concept of both a normal film and a sheet, and may have any dimensions such as shape and thickness. This anti-fogging sheet can be easily attached to an object to be coated, and an excellent anti-fogging performance can be exhibited by the covering. As the synthetic resin film, a polyethylene terephthalate film, a polycarbonate film, or the like is used. Examples of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer include pressure-sensitive adhesives such as acrylate copolymer, natural rubber, styrene-butadiene copolymer rubber (SBR), ethylene-vinyl acetate copolymer, dimethyl silicone, and methylphenyl silicone. Etc. are used.

  When sticking an antifogging sheet | seat to a coating | coated object, it can replace with the said adhesive layer and can also employ | adopt the means by heat sealing | fusion etc. Furthermore, the coating composition can be directly coated on the object to be coated. Specific examples of objects to be coated include synthetic resin molded products, inorganic glass lenses, building windows, bathroom windows, mirrors, automobile or train, aircraft, ship and other vehicle windows, ski goggles, masks, motorcycles, etc. The shield etc. which are used for a helmet etc. are mentioned.

  Now, the coating composition is obtained by mixing (blending) polyalkylene glycol urethane-modified poly (meth) acrylate and urethane-modified poly (meth) acrylate. This coating composition is applied to the surface of the object to be coated. At this time, it is presumed that the urethane-modified poly (meth) acrylate is oriented toward the object to be coated. Accordingly, the urethane-modified poly (meth) acrylate can sufficiently exhibit adhesion performance and the like with respect to the object to be coated, while the polyalkylene glycol urethane-modified poly (meth) acrylate can sufficiently exhibit antifogging performance and the like. In that state, the coating composition is cured by the curing means to form a coating. In this coating, a crosslinked structure is formed by the crosslinking reaction of the bifunctional or polyfunctional monomer in the first reaction raw material and the second reaction raw material of the coating composition.

  As a result, it is estimated that the coated material exhibits adhesion performance to the coated object while exhibiting anti-fogging performance on the surface and also exhibits water resistance performance, weather resistance performance and scratch resistance performance based on the crosslinked structure. The Therefore, according to the coating composition, based on the synergistic action of polyalkylene glycol urethane-modified poly (meth) acrylate and urethane-modified poly (meth) acrylate, anti-fogging performance, water resistance performance, adhesion performance, weather resistance performance and It is possible to obtain a coating that can exhibit the scratch resistance performance in a well-balanced manner.

The effects exhibited by the above embodiment will be described below.
The coating composition of this embodiment contains polyalkylene glycol urethane-modified poly (meth) acrylate and urethane-modified poly (meth) acrylate. For this reason, the antifogging performance possessed by the polyalkylene glycol urethane-modified poly (meth) acrylate and the water resistance performance, adhesion performance, weather resistance performance and scratch resistance performance possessed by the urethane-modified poly (meth) acrylate are the coating object side and the surface side. And works effectively. Therefore, based on the coating composition, a coating capable of exhibiting a good balance of antifogging performance, water resistance performance, adhesion performance, weather resistance performance and scratch resistance performance can be obtained. As a result, it is possible to obtain a coating capable of exhibiting, in a well-balanced manner, performance with high practical value that cannot be obtained with a conventional coating composition on the surface of a coating object such as a synthetic resin, inorganic glass, or metal.

-Since the coating agent composition contains the polyol compound in the 1st reaction raw material or the 2nd reaction raw material, the coating more excellent in the point of abrasion resistance performance and adhesion | attachment performance can be obtained.
In the coating composition, the polyisocyanate compound has a cyclic skeleton, the number of isocyanate groups is 2 to 6, the compound containing a (meth) acryloyl group and a hydroxyl group has a pentaerythritol skeleton, and (meth) The number of acryloyl groups is 1 to 3. For this reason, a crosslinked structure is formed densely, and a coating that is more excellent in terms of scratch resistance, adhesion, and water resistance can be obtained.

  The coating composition has a polyalkylene glycol residue ratio of 20 to 85 mass%, a urethane bond ratio of 3 to 30 mass%, and a (meth) acryloyl group ratio of 0.1 to 30 mass%. . Therefore, in addition to the effects of any one of the first to third inventions, the antifogging performance, the scratch resistance performance, the adhesion performance, and the water resistance performance can be expressed in a well-balanced manner.

  The coating is obtained by curing the coating composition by a curing means such as irradiation with active energy rays or heating. For this reason, the coating can be easily formed on the surface of the coating object, and the coating object can have an excellent anti-fogging function.

  -According to the anti-fogging sheet | seat, the coating material by the coating composition is provided in one side of the synthetic resin film as a coating target object, and the adhesive layer is provided in the other surface. Therefore, the effect of the covering can be exhibited on one surface of the synthetic resin film, and the other surface can be easily attached to the covering object via the pressure-sensitive adhesive layer.

Hereinafter, the embodiment will be described more specifically with reference to synthesis examples, examples, and comparative examples. The physical properties in each example and comparative example were evaluated according to the following measurement methods.
(A) Expiration and anti-fogging performance test Breathing was performed on the object to be coated (coating film) in a temperature-controlled room at a temperature of 20 ° C. and a relative humidity (RH) of 50%, and the cloudy state was visually determined according to the following criteria.
○: No fogging, Δ: Some clouding is observed, ×: The entire surface is cloudy.
(B) Steam anti-fogging performance test A test plate was fixed at a position 1 cm from the water surface on a constant temperature water bath at 60 ° C., and the fogging state after 10 minutes was visually evaluated based on the following criteria.
A: No water droplets, O: No water droplets having a diameter of 5 mm or less, Δ: Partial water droplets having a diameter of 5 mm or less, X: Water droplets having a diameter of 5 mm or less on the entire surface.
(C) Water-resistant performance test It was immersed in a beaker filled with room temperature tap water for 12 hours, taken out, and then left for 24 hours in an atmosphere at a temperature of 20 ° C and a relative humidity (RH) of 50%. Thereafter, an expiratory anti-fogging test was conducted.
(D) Adhesion performance test According to the cross-cut tape method of JIS-K5600, the object to be coated (coating film) is cut in the vertical and horizontal directions at a depth that reaches the substrate with a cutter knife, and 100 crosscuts (cutting) A cellophane adhesive tape (manufactured by Nichiban Co., Ltd., trade name: cellotape) was applied, peeled in a direction perpendicular to the application surface, and the number of crosscuts remaining without peeling was measured.
(E) Scratch resistance test Using # 0000 steel wool on the sample surface, the amount of change (unit:%) in haze before and after rubbing 10 reciprocations under the conditions of a load of 200 g, a width of 25 mm, and a frequency of 50 mm / second was measured. .
(F) Weather resistance performance test The change in yellowness (unit:%) after ultraviolet ray irradiation of 5 J / cm ² was measured with a 120 W high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.).

[Synthesis Example 1, Synthesis of Polyethylene Glycol Urethane Modified Poly (meth) acrylate with 6 Acrylyl Groups, Production Method Based on Processes of Chemical Formulas (4) to (6)]
Isocyanate adduct (4 mol) obtained by adding isophorone diisocyanate (3 molecules) to trimethylolpropane (1 molecule), 2-hydroxyethyl acrylate (hereinafter abbreviated as HEA, 4 mol), dibutyltin dilaurate (hereinafter DBTDL and (Abbreviation, 0.0015 mol), 2,6-di-t-butyl-p-cresol (hereinafter abbreviated as BHT, 0.0015 mol) and 600 g of ethyl acetate were reacted at 60 ° C. for 3 hours.

Subsequently, polyethylene glycol having a mass average molecular weight of 8400 (hereinafter abbreviated as PEG-8400, 3 mol) and ethyl acetate (hereinafter abbreviated as AcOEt, 200 g) were added and reacted at 60 ° C. for 3 hours, and further HEA (2 mol) was added. And reacted at 70 ° C. for 7 hours. By confirming that the absorption characteristic of the isocyanate group appearing at 2250 cm ⁻¹ disappeared by infrared absorption analysis, the reaction was terminated, and the product obtained by removing ethyl acetate was named oligomer A.

[Synthesis example 2, synthesis of polyethylene glycol urethane-modified poly (meth) acrylate having acryloyl group 6 and production method based on the processes of chemical formulas (7) and (8)]
2,6-isophorone diisocyanate (hereinafter abbreviated as IPDI, 4 mol), polyethylene glycol having a mass average molecular weight of 1500 (hereinafter abbreviated as PEG-1500, 3 mol), DBTDL (0.0015 mol) and BHT (0.0015 mol) Was reacted at 60 ° C. for 3 hours. Subsequently, pentaerythritol triacrylate (hereinafter abbreviated as PETA, 2 mol) was added and reacted at 60 ° C. for 12 hours. The reaction was terminated after confirming that the absorption characteristic of the isocyanate group appearing at 2250 cm ⁻¹ disappeared by infrared absorption analysis, and the resulting product was designated as oligomer B.

[Synthesis Example 3, synthesis of polyethylene glycol urethane-modified poly (meth) acrylate having acryloyl group 24, production method based on processes of chemical formulas (1) to (3)]
Isocyanate adduct (7 mol), PEG-600 (6 mol), DBTDL (0.003 mol), BHT (0.0015 mol) and acetic acid obtained by adding tolylene diisocyanate (3 molecules) to trimethylolpropane (1 molecule) 2300 g of ethyl was added and reacted at 60 ° C. for 3 hours. Subsequently, glycerin (1/3 mol) was added and reacted at 60 ° C. for 3 hours. Further, HEA (8 mol) was added and reacted at 60 ° C. for 12 hours. Then, it was confirmed that the absorption characteristic of the isocyanate group appearing at 2250 cm ⁻¹ disappeared by infrared absorption analysis, the reaction was terminated, and the product obtained by removing ethyl acetate was designated as oligomer C.

[Synthesis Example 4, synthesis of urethane-modified poly (meth) acrylate having 9 acryloyl groups, production method based on the process of the chemical formula (14)]
Nutriate compound consisting of 3 molecules of 2,6-isophorone diisocyanate (hereinafter abbreviated as IPDI nurate, 1 mol), PETA (3 mol), DBTDL (0.0005 mol), BHT (0.0005 mol) and MEK 400 g at 60 ° C. For 12 hours. Then, it was confirmed that the absorption characteristic of the isocyanate group appearing at 2250 cm ⁻¹ disappeared by infrared absorption analysis, the reaction was terminated, and the product obtained by removing MEK was designated as urethane A.

[Synthesis Example 5, synthesis of urethane-modified poly (meth) acrylate having acryloyl group 6 and production method based on process of chemical formula (14)]
2,6-isophorone diisocyanate (hereinafter abbreviated as IPDI, 1 mol), PETA (2 mol), DBTDL (0.0005 mol) and BHT (0.0005 mol) were reacted at 60 ° C. for 12 hours. The reaction was terminated after confirming that the absorption characteristics of the isocyanate group appearing at 2250 cm ⁻¹ disappeared by infrared absorption analysis, and the resulting product was designated as urethane B.

[Synthesis Example 6, synthesis of urethane-modified poly (meth) acrylate having acryloyl group 3 and production method based on process of chemical formula (14)]
IPDI nurate (1 mol), HEA (3 mol), DBTDL (0.0005 mol) and BHT (0.0005 mol) were reacted at 60 ° C. for 12 hours. The reaction was terminated after confirming that the absorption characteristics of the isocyanate group appearing at 2250 cm ⁻¹ disappeared by infrared absorption analysis, and the resulting product was designated as urethane C.

[Synthesis Example 7, synthesis of urethane-modified poly (meth) acrylate of acryloyl group 3, production method based on process of chemical formula (14)]
IPDI (3 mol), HEA (3 mol), glycerin (1 mol), DBTDL (0.0005 mol) and BHT (0.0005 mol) were reacted at 60 ° C. for 12 hours. The reaction was terminated after confirming that the absorption characteristics of the isocyanate group appearing at 2250 cm ⁻¹ disappeared by infrared absorption analysis, and the resulting product was designated as urethane D.

[Example 1]
As shown in Table 1, 70% by mass of oligomer A, 30% by mass of urethane-modified poly (meth) acrylate (manufactured by Daicel UCB Co., Ltd., trade name: Ebercy220, number of acryloyl groups: 6), 2-hydroxy- as a photopolymerization initiator A coating composition comprising 3% by mass of 2-methyl-1-phenyl-propan-1-one and methyl ethyl ketone was prepared. Table 2 shows the ratio of polyethylene glycol residues, the ratio of urethane bonds, and the ratio of (meth) acryloyl groups in the coating composition.

  And the coating composition was apply | coated with the bar-coater so that thickness might be set to 10 micrometers on a polyethylene terephthalate. The Ebercy 220 is a urethane-modified poly (meth) acrylate having a benzene ring, a molecular weight of 1000, a (meth) acryloyl group number of 6 (content ratio: 43 mass%), and a urethane bond number of 2 (content ratio: 12 mass%).

Thereafter, the coating composition was cured by irradiating 3 J / cm ² with ultraviolet rays (120 W high-pressure mercury lamp manufactured by Nippon Battery Co., Ltd.) to obtain a coating. Various performance evaluation tests were conducted, and the results are shown in Table 3.

[Example 2]
As shown in Table 1, a coating composition comprising 90% by mass of oligomer A, 10% by mass of Ebercy 2220, 3% by mass of 2-hydroxy-2-methyl-1-phenyl-propan-1-one as a photopolymerization initiator, and methyl ethyl ketone. Was prepared. Table 2 shows the ratio of polyethylene glycol residues, the ratio of urethane bonds, and the ratio of (meth) acryloyl groups in the coating composition.

And the coating composition was apply | coated with the bar coater so that thickness might be set to 20 micrometers on a polyethylene terephthalate. Thereafter, the coating composition was cured by irradiating 3 J / cm ² with ultraviolet rays (120 W high-pressure mercury lamp manufactured by Nippon Battery Co., Ltd.) to obtain a coating. Various performance evaluation tests were conducted, and the results are shown in Table 3.

Example 3
As shown in Table 1, a coating composition comprising 50% by mass of oligomer A, 50% by mass of Ebercy 2220, and 3% by mass of 2-hydroxy-2-methyl-1-phenyl-propan-1-one as a photopolymerization initiator was prepared. did. Table 2 shows the ratio of polyethylene glycol residues, the ratio of urethane bonds, and the ratio of (meth) acryloyl groups in the coating composition.

And the coating composition was apply | coated with the bar coater so that thickness might be set to 30 micrometers on a polyethylene terephthalate. Thereafter, the coating composition was cured by irradiating 3 J / cm ² with ultraviolet rays (120 W high-pressure mercury lamp manufactured by Nippon Battery Co., Ltd.) to obtain a coating. Various performance evaluation tests were conducted, and the results are shown in Table 3.

Example 4
As shown in Table 1, a coating composition comprising 70% by mass of oligomer B, 30% by mass of urethane C, 3% by mass of methyl-2-benzoylbenzoate as a photopolymerization initiator and methyl ethyl ketone was prepared. Table 2 shows the ratio of polyethylene glycol residues, the ratio of urethane bonds, and the ratio of (meth) acryloyl groups in the coating composition.

And the coating composition was apply | coated with the bar coater so that thickness might be set to 20 micrometers on a polyethylene terephthalate. Thereafter, the coating composition was cured by irradiating 3 J / cm ² with ultraviolet rays (120 W high-pressure mercury lamp manufactured by Nippon Battery Co., Ltd.) to obtain a coating. Various performance evaluation tests were conducted, and the results are shown in Table 3.

Example 5
As shown in Table 1, a coating composition comprising 70% by mass of oligomer B, 30% by mass of urethane A, 3% by mass of methyl-2-benzoylbenzoate as a photopolymerization initiator and methyl ethyl ketone was prepared. Table 2 shows the ratio of polyethylene glycol residues, the ratio of urethane bonds, and the ratio of (meth) acryloyl groups in the coating composition.

And the coating composition was apply | coated with the bar coater so that thickness might be set to 20 micrometers on a polyethylene terephthalate. Thereafter, the coating composition was cured by irradiating 3 J / cm ² with ultraviolet rays (120 W high-pressure mercury lamp manufactured by Nippon Battery Co., Ltd.) to obtain a coating. Various performance evaluation tests were conducted, and the results are shown in Table 3.

Example 6
As shown in Table 1, a composition comprising 70% by mass of oligomer C, 30% by mass of urethane B, 3% by mass of methyl-2-benzoylbenzoate as a photopolymerization initiator, and methyl ethyl ketone was prepared. Table 2 shows the ratio of polyethylene glycol residues, the ratio of urethane bonds, and the ratio of (meth) acryloyl groups in the coating composition.

The thickness of the coating composition on a polyethylene terephthalate was coated with a bar coater so that the 20 [mu] m, UV (Japan Storage Battery Co., Ltd. 120W high pressure mercury lamp) to be irradiated with 3J / cm ² to cure the coating A coating was obtained. Various performance evaluation tests were conducted, and the results are shown in Table 3.

Example 7
A composition comprising 70% by mass of oligomer C, 30% by mass of urethane D, 3% by mass of methyl-2-benzoylbenzoate as a photopolymerization initiator, and methyl ethyl ketone was prepared. Table 2 shows the ratio of polyethylene glycol residues, the ratio of urethane bonds, and the ratio of (meth) acryloyl groups in the coating composition.

The thickness of the coating composition on a polyethylene terephthalate was coated with a bar coater so that the 20 [mu] m, UV (Japan Storage Battery Co., Ltd. 120W high pressure mercury lamp) to be irradiated with 3J / cm ² to cure the coating A coating was obtained. Various performance evaluation tests were conducted, and the results are shown in Table 3.

[Comparative Example 1]
As shown in Table 1, a composition comprising 100% by mass of oligomer A and 3% by mass of 2-hydroxy-2-methyl-1-phenyl-propan-1-one as a photopolymerization initiator was prepared. Table 2 shows the ratio of polyethylene glycol residues, the ratio of urethane bonds, and the ratio of (meth) acryloyl groups in the coating composition.

And said composition was apply | coated with the bar-coater so that thickness might be set to 20 micrometers on a polyethylene terephthalate. Subsequently, the composition was cured by irradiating with ultraviolet rays (120 W high pressure mercury lamp manufactured by Nippon Battery Co., Ltd.) 3 J / cm ² to obtain a coating. Various performance evaluation tests were conducted, and the results are shown in Table 3.

[Comparative Example 2]
As shown in Table 1, a composition comprising 100% by mass of urethane A and 3% by mass of 2-hydroxy-2-methyl-1-phenyl-propan-1-one as a photopolymerization initiator is formed on polyethylene terephthalate with a thickness of 20 μm. It applied with a bar coater so that it might become. Subsequently, the composition was cured by irradiating with ultraviolet rays (120 W high pressure mercury lamp manufactured by Nippon Battery Co., Ltd.) 3 J / cm ² to obtain a coating. Various performance evaluation tests were conducted, and the results are shown in Table 3.

表３に示したように、実施例１〜７では、防曇性能、耐水性能、密着性能、耐擦傷性能及び耐候性能のいずれにおいても良好であった。これに対し、比較例１では被覆剤組成物がポリアルキレングリコールウレタン変性ポリ（メタ）アクリレートのみで構成されているため、耐水性能、密着性能及び耐擦傷性能が劣っていることが明らかとなった。比較例２では被覆剤組成物がウレタン変性ポリ（メタ）アクリレートのみで構成されているため、防曇性能が劣っていることが明らかとなった。

As shown in Table 3, in Examples 1 to 7, the antifogging performance, water resistance performance, adhesion performance, scratch resistance performance, and weather resistance performance were all good. On the other hand, in Comparative Example 1, since the coating composition was composed only of polyalkylene glycol urethane-modified poly (meth) acrylate, it became clear that the water resistance, adhesion performance and scratch resistance were inferior. . In Comparative Example 2, since the coating composition was composed only of urethane-modified poly (meth) acrylate, it was revealed that the antifogging performance was inferior.

It should be noted that this embodiment can be implemented with the following modifications.
A second raw material of urethane-modified poly (meth) acrylate can be used, and polyalkylene glycol can be added thereto to form a first raw material of polyalkylene glycol urethane-modified poly (meth) acrylate.

  -Polyalkylene glycol urethane modification by reacting polyisocyanate compound, polyalkylene glycol, compound containing (meth) acryloyl group and hydroxyl group and, if necessary, first reaction raw material mixed with polyol compound using urethanization catalyst Poly (meth) acrylates can also be produced.

  -A urethane-modified poly (meth) acrylate is produced by reacting a second reaction raw material obtained by mixing a polyisocyanate compound, a compound containing a (meth) acryloyl group and a hydroxyl group, and a polyol compound with a urethanization catalyst. You can also.

-In order to improve the adhesion | attachment performance with respect to a coating target object, you may mix | blend the compound which has a carboxyl group etc. with a coating composition.
Further, the technical idea that can be grasped from the embodiment will be described below.

  The coating composition according to any one of claims 2 to 4, wherein the polyisocyanate compound is a compound having 3 or more isocyanate groups, or the polyol compound is a compound having 3 or more hydroxyl groups. When comprised in this way, the coating obtained by hardening | curing a coating composition has a crosslinked structure with many crosslinking points, and can improve water resistance performance, scratch resistance performance, etc.

  The coating composition according to any one of claims 1 to 4, wherein the polyisocyanate compound is a diisocyanate compound or a polyol compound having two hydroxyl groups. When comprised in this way, a coating composition can be made low-viscosity and a coating property can be improved.

Claims (6)

A polyalkylene glycol urethane-modified poly (meth) acrylate obtained by reacting a first reaction raw material containing a polyisocyanate compound, a polyalkylene glycol and a compound containing a (meth) acryloyl group and a hydroxyl group using a urethanization catalyst; It contains a urethane-modified poly (meth) acrylate obtained by reacting a second reaction raw material containing a polyisocyanate compound and a compound containing a (meth) acryloyl group and a hydroxyl group using a urethanization catalyst. Coating composition. The coating composition according to claim 1, wherein the first reaction raw material or the second reaction raw material contains a polyol compound other than polyalkylene glycol. The polyisocyanate compound has a cyclic skeleton, the number of isocyanate groups is 2 to 6, the compound containing a (meth) acryloyl group and a hydroxyl group has a pentaerythritol skeleton, and the number of (meth) acryloyl groups is 1 to 1. The coating composition according to claim 1, wherein the coating composition is 3. The proportion of polyalkylene glycol residues in the coating composition is 20 to 85% by mass, the proportion of urethane bonds is 3 to 30% by mass, and the proportion of (meth) acryloyl groups is 0.1 to 30% by mass. The coating composition according to any one of claims 1 to 3. A coating obtained by curing the coating composition according to any one of claims 1 to 4 by a curing means. An anti-fogging sheet characterized in that the covering according to claim 5 is provided on one surface of a synthetic resin film, and an adhesive layer is provided on the other surface.