JPS6157876B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a white coating composition that cures and dries rapidly by irradiation with active energy rays, particularly Cytoradiation, and has excellent adhesion to substrates and surface gloss. Recently, from the standpoint of environmental conservation and resource conservation, infrared
There is active development of solvent-free resin compositions that harden and dry when irradiated with active energy rays such as ultraviolet rays or ionizing radiation, and are used in a wide range of applications including printing plate materials and printing inks, as well as paints, adhesives, photoresists, and magnetic tapes. It is being put into practical use in the field. Commonly used polymers are mainly composed of oligomers, prepolymers, or monomers having radically polymerizable double bonds, and if necessary, initiators, colorants, etc. are added. Introducing special functional groups into these oligomers or prepolymers to improve curing performance, coating film performance, or storage stability, or investigating optimal initiators to improve the curing performance of resin compositions. The current situation is that they are doing the following. However, when these resin compositions are applied to thin films such as gloss varnishes on printing ink surfaces or vehicles for offset printing inks, the curing speed and surface gloss are significantly lower than those of conventional heat-drying types. Although excellent, depending on the type of substrate to be used, adhesion may be poor or there may be problems with printing performance, so it is not necessarily satisfactory in practical terms. On the other hand, for applications such as white coating and screen printing that require relatively thick films using pigments, especially white pigments, the three main factors are curing performance, surface gloss, coating performance, and especially adhesion to the substrate. Improving performance is technically extremely difficult. For example, when using a commercially available epoxy acrylic resin as a photocurable resin, the curing speed is fast and the surface gloss is excellent, but the adhesion to the substrate is generally poor. For this reason, efforts are being made to modify the resin, consider the types and amounts of monomers and sensitizers used, and even devise methods of light irradiation, but so far they have only been applied to specific base materials. Not successful. In addition, certain acrylic urethane resins exhibit excellent adhesion to all types of substrates, but because they are thick films, their ability to transmit light is limited, resulting in insufficient internal curing and Wrinkles often occur on the film surface. These surface wrinkles are thought to be caused by the difference in speed between internal curing and surface curing, and include the use of sensitizers that are highly sensitive to light in the long wavelength region, which has excellent transmission ability, and the use of monomers that delay surface curing. Although active research is being carried out on the addition of colorants, the particle size of colorants, and surface treatments, there is little that satisfies the practical requirements of curing performance, gloss, and adhesion. Under these circumstances, the present inventors have developed a white material that quickly hardens and dries by irradiation with active energy rays, especially ultraviolet rays, and provides extremely excellent adhesion and surface gloss to non-absorbing surfaces such as metal and glass. As a result of repeated research to obtain a coating composition, the present invention was completed. That is, the present invention relates to a (meth)acrylic urethane having at least one bisphenol skeleton and at least two urethane bonds in the main chain of the molecule, and containing an acryloyl group and/or methacryloyl group at the terminal. A resin [], a monomer having a polymerizable double bond copolymerizable with the terminal unsaturated group introduced into the (meth)acrylic urethane resin [], and a photosensitizer []. The present invention relates to a photocurable white paint composition with excellent adhesion and surface gloss, which is characterized by containing anatase-type titanium oxide [ ] as a main component. Details of each component that can be used in the present invention are shown below. The (meth)acrylic urethane resin [] according to the present invention has at least one bisphenol skeleton and at least two urethane bonds in the main chain of the molecule, and contains a (meth)acryloyl group at the end. , a polyoxyalkylene bisphenol derivative (A), a diisocyanate compound (B), and a hydroxyl group-containing (meth)acrylate compound (C)
Alternatively, it can be synthesized from a polyoxyalkylene bisphenol derivative (A), a diisocyanate compound (B), a hydroxyl group-containing (meth)acrylate compound (C), and a carboxyl group-containing (meth)acrylate compound (D). The polyoxyalkylene bisphenol derivative (A) useful in the present invention can be represented by the following formula (a): (In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms; R ²
is −CH ₂ −,

A hydrocarbon group selected from [Formula]; R ³ is a hydrocarbon group selected from aliphatic, alicyclic or aromatic groups having 2 to 8 carbon atoms; X is a halogen or methyl group; a is an integer of 0 to 2; m
and n are each an integer of at least 1, the sum of which is an integer of 2 to 10; l is an integer of 0 to 2). It can be synthesized by reaction at 140-150℃. Number of moles of alkylene oxide added (m+n)
When is larger than 10, the flexibility of the cured resin coating film finally obtained is improved, but the mechanical properties such as coating film strength are reduced and the curing speed is also slowed. As the polyoxyalkylene bisphenol derivative (A), in addition to the addition reaction product of bisphenol and alkylene oxide, the addition reaction product of bisphenol and alkylene oxide and dicarboxylic acid and/or their acid anhydride are used in a molar ratio of 3. It can also be easily produced by dehydrating and esterifying two or more pairs. If the molar ratio is less than 3 to 2, the molecular weight of the resulting condensation reaction product will be too high, causing inconvenience in subsequent handling, or the resulting resin will have a terminal carboxyl group, making it difficult to obtain the target compound of the present invention. can't get it. The dicarboxylic acids and/or their acid anhydrides used include succinic acid, succinic anhydride, adipic acid, sebacic acid, maleic acid,
Aliphatic dibasic acids represented by maleic anhydride, fumaric acid, itaconic acid, etc., aromatic dibasic acids represented by phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, or hexahydrophthalic acid,
Examples include alicyclic dibasic acids represented by hexahydrophthalic anhydride. In the above dehydration esterification reaction, in addition to the addition reaction product of bisphenol and alkylene oxide as the first glycol component, it is also possible to use a small amount of a glycol component having 2 to 12 carbon atoms as the second glycol component. be. Representative examples of the diisocyanate compound (B) used in the present invention include the following. Namely, tolylene diisocyanate, dienylmethane-4,4'-diisocyanate, phenylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate,
1,6-hexamethylene diisocyanate, 1.
4-tetramethylene diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, hydrogenated tolylene diisocyanate, dimers of these diisocyanates, or addition reactions between these diisocyanates and active hydrogen compounds. It is a product. The hydroxyl group-containing (meth)acrylate compound (C) used in the present invention has the following general formula (B):
Compounds represented by ~(d) can be mentioned. (In the formula, R ₄ is a hydrogen atom or a methyl group; R ⁵ is an alkylene group having 2 to 4 carbon atoms; R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; p is an integer of 1 to 3; q is an integer between 1 and 2). These hydroxyl group-containing (meth)acrylate compounds can be obtained by known methods. If the integer p in the above formula (b) is larger than 3, the final result is obtained (meta)
The coating strength of the acrylic urethane resin [] will decrease and the curing speed will also slow down. Representative examples of the compounds represented by the above general formulas (b) to (d) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and polyoxyethylene (2) (meth)acrylate. , polyoxypropylene(2)(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaesthritol Examples include tri(meth)acrylate.
In addition, a (meth)acrylated polyoxyalkylene bisphenol derivative having a hydroxyl group, which is a reaction product of the above-mentioned polyoxyalkylene bisphenol derivative (A) and acrylic acid or methacrylic acid, can also be used. Examples of the carboxyl group-containing (meth)acrylate compound (D) useful in the present invention include acrylic acid and methacrylic acid;
Equimolar reaction products of the hydroxyl group-containing (meth)acrylate compounds (C) and acid anhydrides of the above (b) to (d) can also be used. There are various methods for producing the desired (meth)acrylic urethane resin [] using the above compounds (A) to (D), but the typical production method is to use the polyoxyalkylene bisphenol derivative (A). , without using any solvent or a suitable reactive diluent, especially the (meth)acrylic urethane resin []
Polymerizability 2 that can be copolymerized with the unsaturated group introduced into
This is a method in which the diisocyanate compound (B) is gradually added in the presence of the monomer [] having a heavy bond to cause substantially all of the isocyanate groups to react. In this case, the ratio of the isocyanate group of the diisocyanate compound (B) to the hydroxyl group of the polyoxyalkylene bisphenol derivative (A) is 1.8 to 5, preferably 2 to 3, and the hydroxyl group-containing (meth)acrylate compound (C) is For 1 mole of polyoxyalkylene bisphenol derivative (A), the following formula c≧(by-x)/z (where c is the number of moles of the hydroxyl group-containing (meth)acrylate compound (C); z is the number of hydroxyl group-containing (meth)acrylate compounds (C); ) Acrylate compound (C)
b is the number of moles of diisocyanate compound (B); y is the number of isocyanate groups in one molecule of diisocyanate compound (B); x is 1 of polyoxyalkylene bisphenol derivative (A) It is desirable to carry out the reaction in an amount that conforms to the number of hydroxyl groups in the molecule. Another typical production method is to produce a (meth)acrylated polyoxyalkylene bisphenol derivative obtained by reacting a polyoxyalkylene bisphenol derivative (A) with a carboxyl group-containing (meth)acrylate compound (A). The method is to go through That is, first, a polyoxyalkylene bisphenol derivative (A) and a carboxyl group-containing (meth)
and acrylate compound (D) in a molar ratio of 1:0.5 to
1.2:2, preferably 1:0.8 to 2:3, obtained by dehydration and esterification, acid value 0 to 10
A partially (meth)acrylated (meth)acrylated polyoxyalkylene bisphenol derivative having a hydroxyl group is synthesized, and then a mixed system of this and a hydroxyl group-containing (meth)acrylate compound (C) is synthesized. This is a method in which the diisocyanate compound (B) is gradually added in the absence of a solvent or in the presence of a suitable reactive diluent to cause substantially all of the isocyanate groups to react. In this case, the ratio of the isocyanate group of the diisocyanate compound (B) to the hydroxyl group of the (meth)acrylated polyoxyalkylene bisphenol derivative is 1.8 to 5, preferably 2 to 3, and the hydroxyl group-containing (meth)acrylate compound (C ) is the following formula for 1 mole of (meth)acrylated polyoxyalkylene bisphenol derivative: c≧(by-w)/z (where c is the number of moles of the hydroxyl group-containing (meth)acrylate compound (C); z is Hydroxyl group-containing (meth)acrylate compound (C)
b is the number of moles of the diisocyanate compound (B); y is the number of isocyanate groups in one molecule of the diisocyanate compound (B); w is the (meth)acrylated polyoxyalkylene bisphenol derivative (representing the number of hydroxyl groups in one molecule). The monomer having a polymerizable double bond used in the present invention [] is a compound having an unsaturated group that can be copolymerized with the (meth)acrylic urethane resin [], and preferable examples include aromatic vinyl compounds, acrylic acid, etc. These include esters, methacrylic esters, vinyl esters, and allyl esters. More preferred are styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, diethylene glycol mono( meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol mono(meth)
Acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol mono(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol mono(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butanediol Mono(meth)acrylate, 1.3
-butanediol di(meth)acrylate, 1.
4-butanediol mono(meth)acrylate,
1,4-butanediol di(meth)acrylate, neopentyl glycol mono(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, 1,6-hexanediol di( meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri (meth)acrylate, pentaerythritol tetra(meth)acrylate, 2-
Ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, reaction product of bisphenol A and ethylene oxide adduct with (meth)acrylic acid, bisphenol A and propylene oxide adduct and (meth)acrylic acid Examples include reaction products with acids, and reaction products between tolylene diisocyanate and 2-hydroxyethyl (meth)acrylate. These can be used alone or in the form of a mixture of two or more. Furthermore, a part of the amount of the monomer having a polymerizable double bond used in the present invention [] can be replaced with a commonly used solvent. Monomers having these polymerizable double bonds []
The amount of (meth)acrylic urethane resin [] and monomer [] can be varied over a wide range from the viewpoint of workability, etc., but from the viewpoint of curing speed, adhesion, and coating performance, the amount of (meth)acrylic urethane resin [] and monomer [] The weight ratio is preferably 20:80 to 95:5.
The ratio is 30:70 or 80:20. The photosensitizer used in the present invention may be any known one, such as benzoin,
Benzoin sensitizers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, α-chlorobenzoin, α-allyl benzoin, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, Michler's ketone , ketone sensitizers such as acetophenone, anthraquinone, 2-methyl-anthraquinone, 1-
Chloroanthraquinone, p-benzoquinone, 1.
Quinone sensitizers such as 4-naphthoquinone, sulfide sensitizers such as tetramethylthiuram monosulfide and phenyl disulfide, and sulfonyl chloride sensitizers such as β-naphthalenesulfonyl chloride and p-chlorobenzenesulfonyl chloride. sensitizers, nitro compound sensitizers such as 2-nitrofluorene and 5-nitroacenaphthene, halogenated hydrocarbon sensitizers such as tetrabromomethane, thioxanthone sensitizers such as 2-chlorothioxanthone, azobisiso Azo sensitizers such as butyronitrile and composite sensitizers prepared by appropriately combining various sensitizers are used. The amount of these photosensitizers used can vary over a wide range, but from the viewpoint of curing speed, film performance, and adhesion, it is preferably 0.5 to 20% of the total composition.
Preferably within the range of weight percentages. The white pigment that can be used in the present invention is titanium oxide having an anatase crystal structure, and if necessary, surface-treated pigments can be used to improve dispersibility and fluidity. Titanium oxide, which has a rutile-type crystal structure, has a greater light absorption ability than anatase-type crystal structure, which is one of its drawbacks.
However, with the development of remarkable irradiation equipment in recent years, this point has been greatly improved, and whiteness and
At present, anatase-type titanium oxide, which has poor hiding properties, is almost ignored. However, as will be clarified in the Examples below, when the film thickness is increased to 20 μm or more, when rutile-type titanium oxide is used, the surface gloss becomes extremely poor even if a powerful irradiation device is used. On the other hand, when forming a thick coating film, the present invention makes it possible to provide excellent surface gloss even when the pigment concentration is significantly increased by using anatase titanium oxide. Further, in the present invention, it is also possible to replace a part of the anatase type titanium oxide with a white extender pigment such as magnesium carbonate. The amount of anatase-type titanium oxide [ ] to be used can vary widely depending on the intended use, but from the viewpoint of curing speed, coating performance, coating condition, etc., it is preferably in the range of 10 to 40% by weight based on the total composition. It is desirable that it be within The non-absorbent polar surface referred to in the present invention is a non-absorbent surface having metal bonds, ionic bonds, coordinate bonds, polar bonds, etc., and the coating composition of the present invention is applied to such surfaces. exhibits extremely excellent adhesion and gloss. Typical non-absorbent polar surfaces include metal surfaces such as steel plates, tin plates, and aluminum plates; polar plastic surfaces such as polyvinyl chloride, polyester resins, acrylic resins, oxidized polyethylene, oxidized polypropylene; Examples include glass surfaces. As described above, the photocurable white paint composition of the present invention has at least one
A (meth)acrylic urethane resin that has at least two bisphenol skeletons and at least two urethane bonds and a (meth)acryloyl group at the end [] and a monomer that has a polymerizable double bond [] It provides excellent adhesion and surface gloss to non-absorbing polar surfaces, which contain as main components a photosensitizer [ ] and anatase-type titanium oxide [ ]. Furthermore, polymerization inhibitors, curing accelerators, fluidity modifiers, waxes, viscosity modulating solvents, various resins, etc. can be added as necessary. The present invention will be explained in more detail below using production examples and examples. All parts in the examples are parts by weight. Production example 1 In a 4-necked flask, add 2.0 mol of propylene oxide 4 mol adduct of bisphenol A and maleic anhydride.
Charge 1.01 mol and raise the temperature to 220°C while blowing _N2 . While keeping the reaction temperature at this temperature,
After reacting until the oxidation level is 8 or less, add hydroquinone to 0.05% by weight (0.51 parts, 0.0047
molar) to prepare polyester glycol. Next, heat this polyester glycol to 100℃.
After cooling to
Perform vacuum dehydration while maintaining at ℃ to reduce water content to 0.07
% by weight or less. After dehydration, cool to 75°C, and while blowing air, 2.0 mol of tolylene diisocyanate (hereinafter abbreviated as TDI) was gradually added dropwise.
React at a temperature range of 75°C to 115°C for 45 minutes, and then
The reaction was continued at 125° C. to 128° C. for 4 hours until the residual NCO% became 0.1% by weight or less to obtain an acrylic urethane resin as a pale yellow transparent solid. Acid value (AV) = 5.8 Hydroxyl value (OHV) = 12.3 NCO% = 0.05 Production example 2 2 mole adduct of propylene oxide of bisphenol A instead of 4 mole adduct of propylene oxide of bisphenol A in the reaction of Production example 1 The same reaction as in Production Example 1 was carried out except that adipic acid was used instead of maleic anhydride to obtain an acrylic urethane resin as a pale yellow transparent solid. AV = 3.3 OHV = 16.8 NCO% = 0.0 Production example 3 In a 4-necked flask, 1.05 moles of 2 moles of ethylene oxide adduct of bisphenol F, 2.02 moles of 2-hydroxypropyl acrylate, and hydroquinone.
0.24 part (0.0022 mol) was added and dehydrated under reduced pressure at 90°C for 30 minutes to reduce the water content to 0.07% by weight or less. Next, cool it to 65℃ and blow air into it.
Add 2.00 mol of TDI dropwise and react for 1 hour in the range of 65°C to 105°C, and then heat the remaining NCO% at 125°C to 127°C.
The reaction was continued for 5 hours until the amount decreased to 0.1% by weight or less to obtain an acrylic urethane resin as a brown transparent solid. AV = 2.5 OHV = 14.4 NOC% = 0.08 Production example 4 In a 4-necked flask, add 1.0 mol of propylene oxide adduct of bisphenol A, 1.0 mol of acrylic acid, and 7.2 parts of p-toluenesulfonic acid (0.038 as monohydrate). mol), 0.35 parts (0.0032 mol) of hydroquinone, and 40 parts (0.43 mol) of toluene were reacted at 120°C in a carbon dioxide gas stream for 6 hours to bring the acid value to 15 or less, and then the reaction temperature was lowered to 70°C and air was blown into the reactor. In this way, AV = 14.3,
A pale brown viscous liquid with OHV=116.4 was obtained. The obtained viscous liquid was dissolved in 300 ml of toluene, extracted five times with aqueous solution 2 consisting of a composition of KOH:NH ₄ Cl: water = 1:15:100 (weight ratio) using a separating funnel, and then further washed with water. The oil layer was washed three times with 1 water. The oil layer thus obtained was transferred to a 4-necked flask, 0.2 parts (0.0018 mol) of hydroquinone was added, and vacuum topping was carried out at 50°C to 60°C for 2 hours. AV = 3.2 OHV = 146.1 Brown moisture % = 0.045 A viscous liquid acrylated polyoxyalkylene bisphenol derivative was obtained. Next, 1.05 mol of the obtained acrylated polyoxyalkylene bisphenol derivative and 1.01 mol of HEA were mixed, and the mixture was heated to 60° C. while blowing air. When the temperature reached 60℃, 1.00 mol of TDI was gradually added dropwise and reacted for 45 minutes at a temperature of 60℃ to 105℃, and then further heated at 125℃ to 128℃ for 3 hours until the residual NCO% was 0.1% by weight or less. The reaction was continued to obtain a brown transparent solid acrylic urethane resin. AV=2.7 OHV=28.1 NCO%=0.01 Production Example 5 2.04 mol of the acrylated polyoxyalkylene bisphenol derivative obtained in Production Example 4 was heated to 60°C in a stream of air, and then 1.00 mol of TDI was gradually added. After dropping and reacting for 45 minutes at 60℃ to 85℃, the remaining NCO% was further heated to 125℃ to 128℃.
The reaction was continued for 5 hours until the concentration became 0.1% by weight or less to obtain a brown transparent solid acrylic urethane resin. AV = 2.7 OHV = 38.6 NOC% = 0 Production example 6 (Resin for comparison) 558 parts (3 epoxy equivalents) of the epoxy resin Epicoat 828 (epoxy equivalent weight 186) manufactured by Ciel and 0.39 parts (0.0035 mol) of hydroquinone were placed in a 4-necked flask. The temperature was raised to 100°C in a stream of air, and then 216.3 parts (3.0 mol) of acrylic acid and 3.9 parts (0.015 mol) of DMP-30 (tridimethylaminomethylphenol, manufactured by Rohm and Haas) were added at room temperature in advance. Gradually drip the mixture for a few minutes,
The reaction was allowed to proceed for 5 hours at a temperature of 115°C to 115°C, and the reaction was terminated when the acid value became 5 or less. The obtained resin was a pale yellow transparent viscous resin. AV = 3.8 Oxirane Oxygen % = 0.19 Production Example 7 (Resin for Comparison) 2.1 mol of HEA and 0.3 parts (0.0027 mol) of hydroquinone were added to a 4-necked flask, and the mixture was heated to 85% in an air stream.
The temperature was raised to ℃, and then 1.0 mol of TDI was gradually added dropwise to react at 85℃ to 90℃ for 30 minutes. The reaction was continued for a period of time to obtain a pale yellow transparent viscous acrylic urethane resin. AV=2.1 OHV=14.8 NCO%=0.05 Example 1 11.6 parts of benzoin isobutyl ether as a photosensitizer and 0.5 parts of hydroquinone as a polymerization inhibitor were added to the resin components, monomer components, and pigments listed in Table 1.
A photo-curable white paint composition was prepared by adding 1.0 parts and uniformly mixing and dispersing the mixture using a ball mill. The obtained composition was coated on acetone-degreased ordinary plate glass (JIS R-3201) using a wire coater.
It was applied to a film thickness of 30μ. Immediately after application, use a high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.) with an intensity of 80w/cm.
It was cured and dried by irradiating ultraviolet light for 10 seconds from a distance of 10.5 cm. The cured coating film was evaluated for pencil hardness, cellophane removability, and surface gloss, and the results are shown in Table 1. For comparison, compositions other than those of the present invention were similarly tested, and the results are also shown in Table 1. In addition, the evaluation of the coating film performance described in Tables 1 to 3 is based on the following method. 1. Pencil hardness: Using a Mitsubishi Uni-pencil with a hardness of 4B to 6H, the coating film was strongly scratched and the maximum hardness without scratches was indicated. 2 Cut cellophane tape removability: cut 11 straight lines on the paint film at 1 mm intervals vertically and horizontally until they reach the surface of the base material, make 100 square cellophores, and then apply cellophane tape (manufactured by Sekisui Chemical) strongly on top of these. It was expressed by the number of squares that remained without peeling when the sellotape was removed instantly. 3 Surface gloss: Gloss meter manufactured by Murakami Color Technology Institute
It is shown as the value of 60° specular reflectance measured using GM-3M.

[Table] Example 2 Acetone-degreased BT#37 treated mild steel plate (JIS G-3141) was used instead of the acetone-degreased ordinary plate glass in Example 1, and the coating and curing were done in the same manner as in Example 1 except for the above. The pencil hardness, cellophane tape removability and surface gloss were evaluated. The formulation and test results are shown in Table 2. For comparison, compositions other than those of the present invention were similarly tested, and the results are also shown in Table 2.

【table】

[Table] Example 3 A tin plate (JIS G-3303) surface-treated with a vinyl sizing agent was used instead of the acetone-degreased ordinary plate glass in Example 1, and the coating was carried out in the same manner as in Example 1. hardened, pencil hardness,
The removability of cellophane tape and surface gloss were evaluated. The formulation and test results are shown in Table 3. For comparison, compositions other than those of the present invention were similarly tested, and the results are also shown in Table 3.

【table】

【table】

Claims (1)

[Claims] Linear formula (In the formula, R ¹ is an alkylene group having 2 to 4 carbon atoms;
R ² is a hydrocarbon group selected from -CH ₂ - and [Formula]; R ³ is an aliphatic group having 2 to 8 carbon atoms;
a hydrocarbon group selected from alicyclic or aromatic, X
is a halogen or a methyl group; a is an integer of 0 to 2; m and n are each an integer of at least 1, the sum of which is an integer of 2 to 10; l is 0
a polyoxyalkylene bisphenol derivative (A) represented by (an integer from 2 to 2), a diisocyanate compound (B), and a hydroxyl group-containing acrylate or methacrylate {hereinafter abbreviated as (meth)acrylate}
obtained by reaction with compound (C) or of formula (a)
A molecule obtained by the reaction of a polyoxyalkylene bisphenol derivative (A) represented by (A), a diisocyanate compound (B), a hydroxyl group-containing (meth)acrylate compound (C), and a carboxyl group-containing (meth)acrylate compound (D) (meth)acrylic urethane resin [] having at least one bisphenol skeleton and at least two urethane bonds in the main chain and containing a (meth)acryloyl group at the terminal; and the (meth)acrylic urethane resin. [] A monomer having a polymerizable double bond that can be copolymerized with the terminal unsaturated group introduced into [], a photosensitizer [], and anatase-type titanium oxide []
A photocurable white paint composition which provides excellent adhesion and surface gloss to non-absorbing polar surfaces, and which contains as a main component. 2 In the polyoxyalkylene bisphenol derivative (A) represented by formula (A), the alkylene group R ¹
The photocurable white paint composition according to claim 1, wherein is an ethylene group or a propylene group. 3. The photocurable white coating composition according to claim 1, wherein (m+n) is 2 to 6 in the polyoxyalkylene bisphenol derivative (A) represented by formula (A). 4 Diisocyanate compound (B) is tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate,
The photocurable white coating composition according to claim 1, which is xylylene diisocyanate or isophorone diisocyanate. 5 The hydroxyl group-containing (meth)acrylate compound (C) is 2-hydroxyethyl (meth)acrylate, 2
-Hydroxypropyl (meth)acrylate, 3
-Chloro-2-hydroxypropyl (meth)acrylate, polyoxyethylene(2)(meth)acrylate, polyoxypropylene(2)(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate and a (meth)acrylated polyoxyalkylene bisphenol derivative having a hydroxyl group obtained by the reaction of the polyoxyalkylene bisphenol derivative (A) and (meth)acrylic acid. A photocurable white coating composition according to Scope 1. 6. The photocurable white paint composition according to claim 1, wherein the carboxyl group-containing (meth)acrylate compound (D) is acrylic acid or methacrylic acid. 7 The (meth)acrylic urethane resin [] has a ratio of the isocyanate group of the diisocyanate compound (B) to the hydroxyl group of the polyoxyalkylene bisphenol derivative (A) of 1.8 to 5, and is a hydroxyl group-containing (meth)acrylate compound (C ) is based on 1 mole of polyoxyalkylene bisphenol derivative (A) c≧(by-x)/z (where c is the number of moles of the hydroxyl group-containing (meth)acrylate compound (C) used; z is the hydroxyl group-containing ( The number of hydroxyl groups in one molecule of the meth)acrylate compound (C); b is the number of moles of the diisocyanate compound (B) used; y is the number of isocyanate groups in one molecule of the diisocyanate compound (B); x is the polyoxyalkylene 2. The photocurable white coating composition according to claim 1, which is obtained by reacting the bisphenol derivative (A) in an amount corresponding to the number of hydroxyl groups in one molecule. 8 (Meth)acrylic urethane resin [] is an acid obtained by condensing a polyoxyalkylene bisphenol derivative (A) and a carboxyl group-containing (meth)acrylate compound (D) at a molar ratio of 1:0.5 to 1.2:2. A method in which the isocyanate group of the diisocyanate compound (B) and The ratio of the (meth)acrylated polyoxyalkylene bisphenol derivative to the hydroxyl group is 1.8 to 5, and the hydroxyl group-containing (meth)acrylate compound (C) is per mole of the (meth)acrylated polyoxyalkylene bisphenol derivative. c≧(by-w)/z (where c is the number of moles of the hydroxyl group-containing (meth)acrylate compound (C) used; z is the number of hydroxyl groups in one molecule of the hydroxyl group-containing (meth)acrylate compound (C); b is the number of moles of the diisocyanate compound (B) used; y is the number of isocyanate groups in one molecule of the diisocyanate compound (B); w is the number of hydroxyl groups in one molecule of the (meth)acrylated polyoxyalkylene bisphenol derivative 2. The photocurable white coating composition according to claim 1, which is obtained by reacting the photocurable white coating composition in such an amount as to satisfy the following: 9. The photocurable white coating composition according to claim 1, wherein the monomer [] having a polymerizable double bond is an aromatic vinyl compound, an acrylic ester, a methacrylic ester, a vinyl ester, or an allyl ester. . 10. The photocurable white coating composition according to claim 1, wherein the weight ratio of the (meth)acrylic urethane resin [] to the monomer [] is from 20:80 to 95:5. 11 The amount of photosensitizer [] used in the whole composition
A photocurable white coating composition according to claim 1, wherein the amount is from 0.5 to 20 weight percent. 12. The photocurable white coating composition according to claim 1, wherein the amount of anatase titanium oxide [] is 10 to 40% by weight based on the total composition.