JP3442540B2 - Article having a hydraulic transfer membrane - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention
Shapes such as patterns formed on the surface of plastic molded products
Excellent scratch resistance by coating the formed printing surface
Curable resin composition imparting high-grade feeling and its use
Surface-treated coatings. 2. Description of the Related Art Conventional techniques include, for example, an automobile interior part.
Finishing of home appliances, home appliances, office supplies, indoor decorations, etc.
One of the processing methods is printing finish by a hydraulic transfer method. This
The hydraulic transfer printing method prints patterns on the surface in advance
Floated special film on the surface of the water
In the state where the ink representing the design etc. is floating on the water surface,
Indications such as plastic moldings made of BS material
Press the printed article against the surface of the water,
The ink of the design etc. is formed into plastic using the water pressure
This is a printing method for transferring to the surface of a mold. The printing surface by such a hydraulic transfer method is one of the following.
Generally water resistance, chemical resistance, weather resistance, external mechanical shock
Because of poor durability and luxury
Usually, the number average molecular weight is 1
Clear coating using more than 000 clear coatings,
Protective coating treatment, such as Lacquer paint and matt clear paint
Has been done. In addition, high durability with high quality
In the case of automotive interior parts, where
Especially after scratching and purple resistance
There is a demand for a protective coating having excellent external characteristics. [0004] However, the hydraulic press
Good adhesion to printed surface and good scratch resistance
It was difficult to apply a protective coating that balances durability and other properties
, Primer treatment before scratch resistance
It was necessary to apply a durable protective coating process such as the above.
For this reason, there were problems in coating cost, productivity, and the like. [0005] Furthermore, the surface of the article is formed by a hydraulic transfer method.
When printing, make sure that the printing
Depending on the shade of the color of the pattern, etc., transferred to the surface of the article
Because there are thick and thin parts (up to 10μ)
m), the conventional paint is applied to such a mark by the usual painting method.
Satisfactory sharpness can be obtained when applied to the printing surface
Coating surface is not as smooth as
In order to obtain a surface,
And then apply a thinner coating once
It is necessary to repeat painting once and three times,
There was a title. [0006] The present invention provides a method for printing on a printing surface by hydraulic transfer.
Good adhesion without primer treatment, and
Satisfactory clarity, luxury, durability and economy
An article having a printing film formed by hydraulic transfer is provided.
You. Means for Solving the Problems The above-mentioned problems are solved.
In order to achieve this, in the invention of claim 1, the surface is transferred by hydraulic transfer.
In the article coated with the printed film formed on the
1 to 100 with respect to 1 mol of a vinyl monomer having a group
Polylacto obtained by reacting mole lactone compound
10 to 100 parts by weight of a monomer compound and 0 to 90 parts by weight of a monomer component
And a polyol resin obtained by copolymerizing
Having a hydroxyl value of ~ 150 mgKOH / g and a number average
PO with a molecular weight of 2,000 or more and 10,000 or less
One equivalent of the hydroxyl group of the riol resin and the polyol resin
And 0.5 to 3.0 equivalents of isocyanate group
Isocyanate compound that can react with
Characterized in that the printing film is coated with a curable resin composition.
To provide an article having a printed film by hydraulic transfer.
is there. An embodiment of the present invention will be described below.
Curable composition is coated on the printing surface by normal hydraulic transfer
Immediately before being performed, a main agent mainly composed of a polyol resin component
And a curing agent mainly containing an isocyanate compound, and
By mixing a thinner mainly composed of solvent
can get. For use in the polyol resin used in the present invention
Examples of the starting materials for the polylactone compounds
For example, hydroxyethyl acrylate, hydroxyethyl
Methacrylate, hydroxybutyl acrylate, hydrate
Roxybutyl methacrylate, hydroxypropyl
Acrylate, hydroxypropyl methacrylate, etc.
Hydroxy having 2 to 8 carbon atoms of lylic acid or methacrylic acid
Alkyl esters and the like. Preferred among these
Or hydroxyethyl acrylate, hydroxyethyl
It is chill methacrylate. [0010] The polylactone compound is used as a starting material for the reaction.
1 to 100 mol, preferably 5 to 20 mol per mol
Β-propiolactone, pivalolactone, γ-butyrate
Lolactone, γ-valerolactone, δ-valerolactone
Lactone compounds such as lactone and ε-caprolactone, preferably
Is ε-caprolactone, β-methyl-δ-valerolacto
100 ° C to 180 ° C, preferably 130 ° C under a catalyst
It is obtained by reacting at a temperature of １５０150 ° C. for 1 to 15 hours. Lactone is used per mole of the above-mentioned reaction starting material.
Using a polylactone compound reacted with 1 mol or less of the compound
When the present curable resin composition is composed,
Is not preferred because the durability of the film cannot be improved. Also before
100 moles of the lactone compound per mole of the reaction starting material
Full curing using a polylactone compound that has reacted
When a water-soluble resin composition is formed, the viscosity of the polyol resin increases.
Rise, and a decrease in stability during low-temperature storage appears.
When applied to an article with a printing surface by hydraulic transfer,
Unevenness occurs on the coated surface due to the density of the ink on the printed surface
High-precision smooth surface cannot be obtained and satisfactory sharpness
Is not preferred. Next, the polylactone compound used in the synthesis
Examples of the catalyst include carboxylic acid, sulfonic acid, and
Organic acids such as phosphoric acid, dibutyltin dilaurate, octyl
Tin luate, dibutyltin oxide, stannous chloride, first bromide
Tin, stannous iodide, tetrabutyl titanate, tetrap
Organic gold such as ropir titanate and tetraethyl titanate
Genus compounds and the like. The polylactone compound obtained by the above method
The compounding ratio in the polyol is 10 to 100 parts by weight.
Is preferred. More preferably, 25 to 50 parts by weight
You. The mixing ratio of the polylactone compound in the polyol is
If the amount is less than 10 parts by weight, the durability, such as scratch resistance, is improved.
It is not preferable because it cannot be improved. A simple copolymerizable with the polylactone compound
Acrylic acid or methacrylic acid
Stels, for example, methyl acrylate, ethyl acrylate
Propyl acrylate, isopropyl acrylate,
Butyl acrylate, hexyl acrylate, octyl acrylate
Chill, lauryl acrylate, methyl methacrylate, meth
Ethyl acrylate, propyl methacrylate, methacrylic acid
Isopropyl, butyl methacrylate, methacrylate
Sil, octyl methacrylate, lauryl methacrylate, etc.
Acrylic acid or methacrylic acid having 1 to 18 carbon atoms
Alkyl ester, methoxybutyl acrylate, methacrylic acid
Methoxybutyl acrylate, methoxyethyl acrylate, meta
Methoxyethyl acrylate, ethoxybutyl acrylate,
Acrylic acid such as ethoxybutyl methacrylate
C2-C18 alkoxyalkyl ester of crylic acid
Alcohol, allyl acrylate, allyl methacrylate, etc.
C2-C8 alkenyl of crylic acid or methacrylic acid
Ester, hydroxyethyl acrylate, hydroxy
Siethyl methacrylate, hydroxybutyl acrylate
G, hydroxybutyl methacrylate, hydroxypro
Pill acrylate, hydroxypropyl methacrylate
Acrylic acid or methacrylic acid such as
Droxyalkyl ester, allyloxyethylacryl
Acrylic acid, allyloxyethyl methacrylate, etc.
Alkenyl having 3 to 18 carbon atoms of phosphoric acid or methacrylic acid
Oxyalkyl esters and the like. Also, vinyl aromatic compounds such as styrene
Len, α-methylstyrene, vinyltoluene, p-chloro
Styrene, polyolefin-based compounds such as butadi
There are also ene, isoprene, chloroprene, etc.
Lilonitrile, methacrylonitrile, methyl isoprope
Nyl ketone, vinyl acetate, vinyl propionate, vinyl
Lupivalate, acrylamide, N-methylol acrylic
L-amide, N-methylol methacrylamide, N-methyl
Roll acrylamide butyl ether, dimethylamino
Ethyl methacrylate, diethylaminoethyl methacrylate
Rate, acrylic acid, methacrylic acid, itaconic acid,
Examples include tonic acid, allyl alcohol, and maleic acid. The polyol resin used in the present invention is generally
Same as ordinary synthetic reaction of acrylic resin or vinyl resin
Method and conditions. One such synthesis reaction
As an example, each monomer component is dissolved in an organic solvent and the radical
About 60 to 180 ° C under a nitrogen atmosphere in the presence of a polymerization initiator
There is a method of heating while stirring at a temperature of about. The reaction
The time is usually about 1 to 10 hours, and the organic solvent
Ether solvents, ester solvents, hydrocarbon solvents
A medium can be used. As the radical polymerization initiator, those usually used are
Can be used, for example
Is benzoyl peroxide, t-butylperoxy-2-e
Peroxide such as tyl hexanoate, azobisisobutyro
Azotization of nitrile, azobisdimethylvaleronitrile, etc.
There are compounds. The polyol resin used in the present invention has a number of
The average molecular weight is preferably from 2,000 to 10,000, more preferably
Preferably the number average molecular weight is 3,000-6,000
You. When the number average molecular weight is less than 2,000,
Solvent resistance of the curable composition, durability such as chemical resistance is reduced,
Printed surface durability of articles with printed surface by hydraulic transfer
It is not preferable because the properties cannot be sufficiently increased.
When the number average molecular weight exceeds 10,000, poly
Increased viscosity of all resin, low surface flatness after coating
Occurs on the printed surface of the product by hydraulic transfer.
When cloth is applied, the coated surface is
Smooth surface cannot be obtained due to unevenness
It is not preferable because the obtained sharpness cannot be obtained. The hydroxyl resin of the polyol resin used in the present invention
The base value is preferably from 50 to 150 mgKOH / g, and more preferably
Preferably, it is in the range of 80 to 120 mgKOH / g.
When the hydroxyl value is less than 50 mgKOH / g, the curable composition
Poor durability such as solvent resistance, chemical resistance, and scratch resistance of the product
Is not preferred. Hydroxyl value is 150mgKOH /
g, the recoating property decreases and the pot life is extremely high.
Problems such as shortening occur, which is not preferable. The isocyanate compound used in the present invention
As the product, for example, hexamethylene diisocyanate,
Isophorone diisocyanate, tolylene diisocyanate
G, 4,4′-diphenylmethane diisocyanate,
4,4'-methylenebis (cyclopexyl isocyanate
G), Burettes such as xylylene diisocyanate
IP adduct, isocyanuric ring type, with polyhydric alcohol
Additives and the like. Of these, hexamethylene is preferred.
Diisocyanate, isophorone diisocyanate,
4,4'-methylenebis (cyclopexyl isocyanate
View of non-yellowing type diisocyanate compounds
-Let type adduct, isocyanuric ring type, polyvalent
It is a rucol adduct. The curable resin composition of the present invention may contain
For example, polyester resin, alkyd resin, epoxy resin
Mix with resin, acrylic resin, cellulose resin, etc.
However, their amounts are only necessary to maintain the effect of the present invention.
For this reason, it is preferable not to exceed 30% by weight. Further, the curable resin composition of the present invention comprises
If necessary, known coating surface adjusters, fluidity adjusters, ultraviolet
Line absorber, light stabilizer, curing catalyst, extender pigment, color pigment,
Can add metal pigment, mica powder pigment, dye etc.
You. [0024] The curable resin composition of the present invention generally comprises an organic compound.
Used after dilution with a solvent. Preferred organic solvents
Is, for example, hydrocarbon solvents such as toluene and xylene,
Keto such as methyl ethyl ketone and methyl isobutyl ketone
Solvents, ester solvents such as ethyl acetate and butyl acetate
Agent, dioxane, ethylene glycol diethyl ether
And the like. these
Can be used alone or as a mixture. The curable resin composition of the present invention may be, for example,
General coating methods such as lay coating, roll coating, brush coating, etc.
Can be painted by The curable resin composition of the present invention is used at a temperature of 100 ° C. or lower.
It can be easily cross-linked and cured even at low temperatures below.
For example, when heating to a temperature of about 50 to 100 ° C., 1
It can be cured in about 0 minutes to 3 hours. Next, Examples 1 to 8 and Comparative Examples 1 to
The present invention will be specifically described with reference to Comparative Example 3.
They are not intended to limit the invention. Example 1 (Synthesis of Polylactone Compound A) Four ports equipped with an air inlet tube, a thermometer, a cooling tube, and a stirrer
Add 2-hydroxyethyl methacrylate 130 to the flask.
Parts, ε-caprolactone 230 parts, hydroquinone mono
Add 1 part of methyl ether and 0.03 part of stannous chloride and empty
The reaction was carried out at a temperature of 120 ° C. for 8 hours while passing air.
Lactone compound A was obtained. (Synthesis of Polyol Resin) A nitrogen introduction tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device were used.
240 parts of toluene and xylene 2 in a four-necked flask equipped with
Forty parts were charged and heated to a temperature of 120 ° C. Adjust separately
93.6 parts of methyl methacrylate, 96 parts of styrene,
68.6 parts of 2-hydroxyethyl acrylate, methacryl
121 parts of normal butyl acid, polylactone compound A96
Parts, 4.8 parts of methacrylic acid, tertiary butyl peroxide
Mixture consisting of 38.4 parts of xy-2-ethylhexanoate
Put the material in a flask using a dropping funnel for 2 hours.
Was added. After the addition is completed, every 20 minutes for 100 minutes
Tert-butyl peroxy 2-ethylhexanoe
2 parts were added a total of 5 times. For another 100 minutes
Finish the reaction by keeping the temperature inside the flask at 120 ° C
did. The hydroxyl value of the obtained polyol resin is 100 mg.
KOH / g. (Preparation of Curable Resin Composition) 75 parts of a polyol resin, 10 parts of methyl ethyl ketone,
Mix 15 parts of ruene and 0.01 part of dibutyltin dilaurate
In this way, a clear resin composition was obtained. Separately, TPA-100 (made by Asahi Kasei Corporation)
Isocyanuric ring type of samethylene diisocyanate
30 parts, 24A-100 (Asahi Kasei)
Buret of hexamethylene diisocyanate manufactured by
Addition type isocyanate compound) 30 parts, toluene
20 parts of ethyl acetate and 20 parts of ethyl acetate were mixed to obtain a curing agent. Separately, 20 parts of ethyl acetate, methyl isobutyl
30 parts, toluene 30 parts, Solvesso 150 (hydrocarbon
(System mixed solvent) was mixed to obtain a thinner. One equivalent of the hydroxyl group contained in the clear resin is
The curing agent was blended at a ratio of 1.2 equivalents with respect to
11.5 seconds viscosity at 25 ° C with Ford Cup # 4
Diluted with the thinner until the curable resin composition
Obtained. (Painting and drying) Wood-grain printing is performed on the ABS molding material by hydraulic transfer method.
Curable resin diluted with the thinner
The composition has a dry film thickness of approximately 25 by air spray coating.
The coating was performed uniformly to a thickness of μm. End of air spray
After leaving, let stand for 5 minutes, and in a box-type drying oven at 80 ° C for 30 minutes.
Drying for minutes was performed. In addition, leave at room temperature for one week
To complete the drying process. Example 2 (Synthesis of polylactone compound B) Four ports equipped with an air inlet tube, a thermometer, a cooling tube, and a stirrer
Add 2-hydroxyethyl methacrylate 130 to the flask.
Part, 570 parts of ε-caprolactone, hydroquinone mono
Add 1 part of methyl ether and 0.06 part of stannous chloride and empty
Reaction for 8 hours at a temperature of 120 ° C while passing air
Kuton compound B was obtained. (Synthesis of Polyol Resin) A nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device were installed.
240 parts of toluene and xylene 2 in a four-necked flask equipped with
Forty parts were charged and heated to a temperature of 120 ° C. Adjust separately
134.4 parts of methyl methacrylate, styrene 96
Part, 2-hydroxyethyl acrylate 80.6 parts, meta
Normal butyl acrylate 68.2 parts, polylactone compound
Material B 96 parts, methacrylic acid 4.8 parts, tertiary butyl
From 38.4 parts of luperoxy 2-ethylhexanoate
The mixture was stirred for 2 hours using a dropping funnel.
It was added into the scoop. After addition, 100 minutes every 20 minutes
Tert-butyl peroxy-2-ethyl
2 parts of xanoate were added a total of 5 times. In addition, 100
Keep the temperature in the flask at 120 ° C for minutes
Finished. The hydroxyl value of the obtained polyol resin is 10
It was 0 mgKOH / g. (Preparation of Curable Resin Composition) As in Example 1. (Coating and Drying) As in Example 1. Example 3 (Synthesis of Polylactone Compound C) Four ports equipped with an air inlet tube, a thermometer, a cooling tube, and a stirrer
58 parts of 2-hydroxyethyl methacrylate in a flask,
427 parts of ε-caprolactone, hydroquinone monomethyl
1 part of ether and 0.05 parts of stannous chloride
The reaction was carried out at a temperature of 120 ° C for 8 hours.
Compound C was obtained. (Synthesis of Polyol Resin) A nitrogen introducing pipe, a thermometer, a cooling pipe, a dropping funnel, and a stirring device were used.
120 parts toluene and xylene 1 in a four-necked flask equipped
20 parts were charged and heated to a temperature of 120 ° C. Adjust separately
72.0 parts of styrene, tert-butyl methacrylate
28.6 parts, 2-ethylhexyl methacrylate
0 parts, 34.0 parts of 2-hydroxyethyl methacrylate,
72.0 parts of polylactone compound C, 2.4 of methacrylic acid
Part, tert-butyl peroxy 2-ethylhexano
Using a dropping funnel, a mixture consisting of 19.2 parts of ate
Added to flask over 2 hours. After the addition,
Tertiary butyl powder every 20 minutes for 100 minutes
-Oxy 2-ethylhexanoate 1 part added 5 times in total
did. In addition, the temperature in the flask for 100 minutes
At 120 ° C. to terminate the reaction. The resulting polio
The hydroxyl value of the toluene resin was 80 mgKOH / g. (Preparation of Curable Resin Composition) As in Example 1. (Coating and Drying) As in Example 1. Example 4 (Synthesis of polylactone compound D) Four ports equipped with an air inlet tube, a thermometer, a cooling tube, and a stirrer
58 parts of 2-hydroxyethyl methacrylate in a flask,
570 parts of ε-caprolactone, hydroquinone monomethyl
1 part of ether and 0.06 part of stannous chloride
The reaction was carried out at a temperature of 120 ° C for 8 hours.
Compound D was obtained. (Synthesis of Polyol Resin) A nitrogen introduction tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device were used.
240 parts of toluene and xylene 2 in a four-necked flask equipped with
Forty parts were charged and heated to a temperature of 120 ° C. Adjust separately
158.8 parts of methyl methacrylate, 96.0 of styrene
Part, normal butyl methacrylate 8.6 parts, methacryl
62.3 parts of 2-hydroxyethyl acid, polylactone compound
Product D148.8 parts, methacrylic acid 4.8 parts, tertiary
-Butyl peroxy 2-ethylhexanoate 38.4
Part of the mixture for 2 hours using a dropping funnel.
Into the flask. After the addition, add 10 minutes every 20 minutes.
Tertiary butyl peroxy 2-E for 0 minutes
One part of tyl hexanoate was added a total of 5 times. further,
Keep the temperature in the flask at 120 ° C for 100 minutes.
To complete the reaction. Hydroxyl group of the obtained polyol resin
The value was 60 mg KOH / g. (Preparation of Curable Resin Composition) As in Example 1. (Coating and Drying) As in Example 1. Example 5 (Synthesis of Polyol Resin) A nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device were used.
120 parts toluene and xylene 1 in a four-necked flask equipped
20 parts were charged and heated to a temperature of 120 ° C. Adjust separately
72.0 parts of styrene, tert-butyl methacrylate
27.6 parts, 2-ethylhexyl methacrylate 28.
8 parts, 37.2 parts of 2-hydroxyethyl methacrylate,
72.0 parts of the polylactone compound D obtained in Example 4,
2.4 parts of crylic acid, tertiary butyl peroxy 2-
A mixture consisting of 19.2 parts of ethyl hexanoate was added dropwise.
Add into flask over 2 hours using funnel
Was. After the end of the addition, add
Shary butyl peroxy 2-ethylhexanoate 1
Were added a total of 5 times. For another 100 minutes
The reaction was completed while maintaining the temperature in the flask at 120 ° C.
The hydroxyl value of the obtained polyol resin is 80 mgKOH /
g. (Preparation of Curable Resin Composition) As in Example 1. (Coating and Drying) As in Example 1. Example 6 (Synthesis of Polyol Resin) A nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device were used.
120 parts toluene and xylene 1 in a four-necked flask equipped
20 parts were charged and heated to a temperature of 120 ° C. Adjust separately
72.0 parts of styrene, tert-butyl methacrylate
30.0 parts, 2-hydroxyethyl methacrylate 4
6.8 parts, polylactone compound D88.
8 parts, 2.4 parts of methacrylic acid, tertiary butyl par
A mixture consisting of 19.2 parts of oxy-2-ethylhexanoate
The mixture was placed in a flask for 2 hours using a dropping funnel.
Was added. After the addition was over, every 20 minutes for 100 minutes
Tert-butyl peroxy 2-ethylhexano
One part of Eat was added a total of 5 times. In addition, in 100 minutes
Keep the temperature inside the flask at 120 ° C for
Done. The hydroxyl value of the obtained polyol resin is 100 m
gKOH / g. (Preparation of Curable Resin Composition) As in Example 1. (Coating and drying) As in Example 1. Example 7 (Synthesis of Polyol Resin) A nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device were used.
120 parts toluene and xylene 1 in a four-necked flask equipped
20 parts were charged and heated to a temperature of 120 ° C. Adjust separately
48.0 parts of styrene, tert-butyl methacrylate
18.7 parts, 2-ethylhexyl methacrylate
4 parts, 50.8 parts of 2-hydroxyethyl methacrylate,
88.8 parts of the polylactone compound D obtained in Example 4, meta
2.4 parts of crylic acid, tertiary butyl peroxy 2-
A mixture consisting of 19.2 parts of ethyl hexanoate was added dropwise.
Add into flask over 2 hours using funnel
Was. After the end of the addition, add
Shary butyl peroxy 2-ethylhexanoate 1
Were added a total of 5 times. For another 100 minutes
The reaction was completed while maintaining the temperature in the flask at 120 ° C.
The hydroxyl value of the obtained polyol resin is 120 mgKOH
/ G. (Preparation of Curable Resin Composition) As in Example 1. (Coating and Drying) As in Example 1. Example 8 (Synthesis of Polylactone Compound E) Four ports equipped with an air inlet tube, thermometer, cooling tube and stirrer
In the flask, add 2-hydroxyethyl methacrylate 29
Part, 570 parts of ε-caprolactone, hydroquinone mono
Add 1 part of methyl ether and 0.06 part of stannous chloride and empty
The reaction was carried out at a temperature of 120 ° C. for 8 hours while passing air.
Lactone compound E was obtained. (Synthesis of Polyol Resin) A nitrogen introducing tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device were used.
240 parts of toluene and xylene 2 in a four-necked flask equipped with
Forty parts were charged and heated to a temperature of 120 ° C. Adjust separately
144.0 parts of styrene, tertiary methacrylate
56.2 parts of chill, 2-hydroxyethyl methacrylate 1
02.2 parts, polylactone compound E172.8 parts, meta
4.8 parts of crylic acid, tertiary butyl peroxy 2-
A mixture consisting of 38.4 parts of ethyl hexanoate is added dropwise.
Add into flask over 2 hours using funnel
Was. After the end of the addition, add
Shary butyl peroxy 2-ethylhexanoate 2
Were added a total of 5 times. For another 100 minutes
The reaction was completed while maintaining the temperature in the flask at 120 ° C.
The hydroxyl value of the obtained polyol resin is 100 mg KOH
/ G. (Preparation of Curable Resin Composition) As in Example 1. (Coating and Drying) As in Example 1. Comparative Example 1 (Synthesis of Polyol Resin) A nitrogen inlet tube, a thermometer, a cooling tube, a dropping funnel and a stirring device were used.
240 parts of toluene and xylene 2 in a four-necked flask equipped with
Forty parts were charged and heated to 120 ° C. Meta adjusted separately
123.3 parts of methyl acrylate, 96.0 parts of styrene,
Normal butyl acrylate 108.4 parts, methacrylic acid
48.0 parts of 2-ethylhexyl, 2-hydroacrylic acid
99.4 parts of xylethyl, 4.8 parts of methacrylic acid,
Butyl peroxy 2-ethylhexanoate 3
The mixture consisting of 8.4 parts was added in 2 hours using a dropping funnel.
Added throughout the flask. After addition, every 20 minutes
Tert-butyl peroxy for 100 minutes
Two parts of 2-ethylhexanoate were added a total of 5 times. Sa
In addition, the temperature in the flask was set to 120 for 100 minutes.
The reaction was terminated by keeping at ℃. Of the obtained polyol resin
The hydroxyl value was 100 mgKOH / g. (Preparation of Curable Resin Composition) As in Example 1. (Coating and Drying) As in Example 1. Comparative Example 2 (Synthesis of Polyol Resin) A nitrogen introducing tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device were used.
240 parts of toluene and xylene 2 in a four-necked flask equipped with
Forty parts were charged and heated to 120 ° C. Meta adjusted separately
252.9 parts of methyl acrylate, 96.0 parts of styrene,
3.0 parts of normal butyl acrylate, 2-phenyl acrylate
123.3 parts of droxybutyl, 4.8 parts of methacrylic acid,
Tertiary butyl peroxy 2-ethylhexanoe
28.4 parts of a mixture consisting of 38.4 parts
Was added into the flask over a period of time. After the addition is completed, 20
Tertiary butyl peroxide for 100 minutes every minute
Add 2 parts of xy-2-ethylhexanoate 5 times in total
Was. In addition, the temperature inside the flask is
The reaction was completed while maintaining the temperature at 120 ° C. The obtained polyol
The hydroxyl value of the resin was 100 mgKOH / g. (Preparation of Curable Resin Composition) As in Example 1. (Coating and Drying) As in Example 1. Comparative Example 3 (Synthesis of Polyol Resin) A nitrogen introducing tube, a thermometer, a cooling tube, a dropping funnel, and a stirring device were used.
240 parts of toluene and xylene 2 in a four-necked flask equipped with
Forty parts were charged and heated to 120 ° C. Meta adjusted separately
123.3 parts of methyl acrylate, 96.0 parts of styrene,
Normal butyl acrylate 108.4 parts, methacrylic acid
48.0 parts of 2-ethylhexyl, 2-hydroacrylic acid
152.0 parts of xylethyl, 4.8 parts of methacrylic acid,
Shary butyl peroxy 2-ethylhexanoate 3
The mixture consisting of 8.4 parts was added in 2 hours using a dropping funnel.
Added throughout the flask. After addition, every 20 minutes
Tert-butyl peroxy for 100 minutes
Two parts of 2-ethylhexanoate were added a total of 5 times. Sa
Furthermore, the temperature in the flask was set to 120 ° C. for 100 minutes.
To end the reaction. Water of the obtained polyol resin
The acid value was 150 mgKOH / g. (Preparation of Curable Resin Composition) As in Example 1. (Coating and Drying) As in Example 1. Next, the above Examples 1 to 8 and ratios
Regarding the results of various tests performed on Comparative Examples 1 to 3,
The results are shown in Table 1 below. As can be seen from this table,
The test results of Examples 1 to 8 are excellent. In Table 1, ◎
Excellent, は indicates good, Δ indicates normal, and × indicates bad. [Table 1] * 1: Cross cut cellophane tape peeling test method. * 2: 50 ° C, 95 RH%, 10 days later. Cross cut
Cellophane tape peel test. * 3: Used by Mitsubishi Uni. * 4: Sandfall test method. Relative evaluation using 2 kg of dry sand. * 5: Recoat after standard paint drying. Cross cut cellophane
Tape peel test. * 6: Relative evaluation test at 30 ° C storage after mixing the curing agent. * 7: Relative evaluation at 500 hours of fade meter. * 8: Visual judgment. The polyol trees of Comparative Examples 1 to 3
The fat has a number average molecular weight of 3,000 to 10,000.
0 was used, the finished appearance was also compared with each example
In the example, the result is “good”, but the number average molecular weight is 10,000.
Apply the conventional general clear paint over 0 in one application
Compared to the case where it is done, not only the finished appearance, but also
The sex is clearly better. As described above, according to the present invention, the hydraulic pressure
Apply a primer treatment to the printing surface by transfer in advance.
It adheres firmly even without it, and provides satisfactory clarity, luxury,
Has a printing film by hydraulic transfer that balances durability and economy
Goods can be provided.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-248799 (JP, A) JP-A-60-165300 (JP, A) JP-A-63-197685 (JP, A) JP-A-62-1979 253671 (JP, A) JP-A-62-252473 (JP, A) JP-A-62-152841 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B44C 1 / 165-1 / 175

Claims (1)

(57) [Claim 1] In an article in which a printed film formed on the surface by hydraulic transfer is coated with a curable resin composition, an amount of 1 to 1 mol of a hydroxyl group-containing vinyl monomer is used. ~ 1
10 to 100 parts by weight of a polylactone compound obtained by reacting 00 mol of a lactone compound with 0 to 90 of a monomer component
A polyol resin having a hydroxyl value of 50 to 150 mg KOH / g and a number average molecular weight of 2,000 or more and 10,000 or less; And a curable resin composition comprising: an isocyanate compound containing 0.5 to 3.0 equivalents of isocyanate groups with respect to 1 equivalent of hydroxyl groups of the resin; Article having a film.