JPS6332825B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition for process release paper, and more specifically, synthetic leather is produced from urethane resin, vinyl chloride resin, polyamide resin, amino acid resin, etc. by a casting method or the like. This is a release agent composition for process paper used during manufacturing, and is a new release agent composition that has not only general quality as a process release agent but also excellent release properties, especially release properties at high temperatures, and gloss. be.

Conventionally, resin compositions for making the surface of processing paper releasable (peelable) include polypropylene,
Three types are known as representative ones: amino alkyd resin type and silicone type. however,
Polypropylene-based materials have excellent removability properties when used repeatedly, but there is a limit to their use at relatively high temperatures. ) type products (synthetic leather, etc.) cannot be obtained.

On the other hand, aminoalkyd resins have excellent gloss but poor releasability, and silicone resins have excellent releasability but are unsuitable for enamel-type synthetic leather because of poor gloss. It has some drawbacks such as:

The present invention aims to provide a novel release agent composition for obtaining a process release paper that has excellent heat resistance, good gloss (products with excellent gloss can be obtained), and has good release properties. This is the general formula [Here, Me is a methyl group, Ph is a phenyl group,
m, n are positive integers, m+n is 30 to 1000, R ¹ represents an organic group, at least one of which has the formula HO
-R-(S) ₂ -R- (where R is a divalent hydrocarbon group having 1 to 10 carbon atoms, and a is 0 or 1); 100 parts by weight of a silicone-modified alkyd resin modified with an organopolysiloxane in which 15 to 50 mol% of organic groups bonded to atoms are phenyl groups, (b) Alkanol-modified amino resin
15 to 150 parts by weight, and (iii) 1 to 20 parts by weight of an acidic catalyst.

The present invention will be explained in detail below.

Component (a) used in the present invention is a silicone-modified alkyd resin, and in the silicone used for this modification, 15 to 50 mol% of the organic groups bonded to silicon atoms in one molecule are phenyl groups. , and at least one of the remaining organic groups is a hydroxy group-substituted organic group represented by the formula HO—R—(S) _a —R— () (R and a are as described above) However, the remaining organic group may be any alkyl group such as a methyl group, ethyl group, or octyl group, or an alkyl group substituted with a halogen group, a cyano group, or the like.

This organopolysiloxane has excellent heat resistance, has good gloss, and achieves the object or effect of the present invention of obtaining good process releasability, so it is expressed by the following general formula. be done.

In the above formula, Me represents a methyl group, Ph represents a phenyl group, m and n are positive integers, and m+n is from 30 to
It is more preferably 50 to 200 than 1000. R ¹ represents an organic group, at least one of which is a hydroxy group-substituted organic group represented by the above formula (),
And the phenyl group in the total organic groups is 15 to 50 mol%. The remaining groups of R ¹ are methyl group, ethyl group,
Any of an alkyl group such as an octyl group, an alkyl group substituted with a halogen, a cyano group, etc. may be used.

In the present invention, the amount of phenyl groups in the organopolysiloxane is set to 15 to 50 mol%, and at least one of the remaining organic groups is a hydroxy group-substituted organic group represented by the above formula (). This is because by using such an organopolysiloxane, performance such as releasability, gloss, and repellency against synthetic leather resins can be satisfied.

R in the hydroxy group-substituted organic group of formula () above
is a divalent hydrocarbon group, a represents 0 or 1, and such organic groups include -CH ₂ CH ₂ -, -
CH ₂ CH ₂ CH ₂ —, —(CH ₂ ) _b —S—(CH ₂ ) _c —
(b is 1 or 2, c is 2 or 3) is exemplified.

The method for obtaining the silicone-modified alkyd resin, which is component (a), using the above organopolysiloxane is mainly (1) the usual synthesis reaction to obtain the alkyd resin, that is, the combination of polyhydric alcohol, fatty acid, polybasic acid, etc. There are two methods: (2) a method in which the organopolysiloxane is reacted simultaneously as an alcohol component when reacting the alkyd resin, and (2) a method in which the organopolysiloxane is reacted with a general alkyd resin synthesized in advance.

The fatty acids used in method (1) may be any of those conventionally used in the production of alkyd resins, including saturated fatty acids such as octyl acid, lauric acid, and palmitic acid, coconut oil, and coconut oil. Examples include unsaturated oils and unsaturated oil fatty acids such as fatty acids, castor oil, castor oil fatty acids, soybean oil, soybean oil fatty acids, etc.; Preferably 20-40
is appropriate. Examples of polybasic acids include phthalic anhydride, isophthalic acid, adipic acid, maleic anhydride, fumaric acid, and trimellitic anhydride. Note that benzoic acid may also be used in combination.

Examples of polyhydric alcohols include glycols such as ethylene glycol, diethylene glycol, propylene glycol, and neopentyl glycol, glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol.

For method (1), a general method may be used in which components such as fatty acids and polybasic acids, polyhydric alcohols, and organopolysiloxane are mixed in a predetermined ratio and subjected to a heating condensation reaction. Components such as basic acids and organopolysiloxane are first reacted,
A method may also be used in which a polyhydric alcohol and a polybasic acid are then added and the condensation reaction is carried out again by heating. The reaction ratio is preferably such that the ratio of components such as fatty acids and polybasic acids to polyhydric alcohol is such that the OH/COOH equivalent is 1.0 to 1.6, preferably 1.2 to 1.4, and the organopolysiloxane is 0.1 to 0.1 to silicone-modified alkyd resin solids content
It is desirable to use it in an amount of 50% by weight, preferably 1 to 40% by weight. The reaction temperature may be determined according to the temperature at which general alkyd resins are synthesized, and 180 to 230°C is usually appropriate.

Next, method (2) is carried out by reacting a synthesized general alkyd resin with organopolysiloxane.The alkyd resin used at this time has an oil length of 0 to 60, preferably 20 to 40. , acid value 1-30 preferably 5-25, hydroxyl value 50-50
Those produced using coconut oil or coconut oil fatty acids, soybean oil or soybean oil fatty acids, castor oil, castor oil fatty acids, rice bran oil fatty acids having a concentration of 300 and preferably 1000 to 3000 are desirable.

The reaction temperature for reacting organopolysiloxane with such alkyd resin is usually 60 to 200℃.
The temperature is preferably 100 to 180°C, and the progress of the reaction can be confirmed by measuring the viscosity, acid value, and hydroxyl value at any time. Therefore, the heating condensation reaction may be continued until these values reach the desired values. The amount of organopolysiloxane to be used is the same as in the case of method (1) above, based on the solid content of the silicone-modified alkyd resin finally obtained.
It is desirable that the content be 0.1 to 50% by weight, preferably 1 to 40% by weight.

Note that when carrying out method (2), there is no problem in using a small amount of an amino resin or the like in combination with the alkyd resin.

As the alkanol-modified amino resin which is the component (b), any commercially available ones can be used, including methoxymethylol melamine resin, butoxymethylol melamine resin, butoxymethylol urea-melamine resin, etc. Examples include condensation resin and butoxymethylolbenzogeanamine resin.

Further, as the acidic catalyst which is the component (iii), any catalyst such as para-toluenesulfonic acid or hydrochloric acid which is usually used for amino alkyd resins may be used.

The blending ratio of component (a), component (b), and component (c) is determined according to the purpose of the present invention, that is, to produce a resin composition for process release paper that has excellent heat resistance, good gloss, and good releasability. From the standpoint of obtaining ingredients, per 100 parts by weight of component (A), 15 to 150 parts by weight of component (B), and 1 to 20 parts by weight of component (C).
It is preferable to use parts by weight. Outside these ranges, the above-mentioned preferred physical properties cannot be obtained.

In addition, the resin composition for process release paper of the present invention includes:
If necessary, ordinary alkyd resins, acrylic resins, silicone-modified acrylic resins, etc. may be blended.

The resin composition of the present invention is usually conveniently used as a solvent solution, and the solvent used for this purpose is one that does not have reactivity with the components (a) and (b). For example, one or a mixture of two or more of benzene, toluene, xylene, methanol, ethanol, isobutanol, n-butanol, methyl ethyl ketone, acetone, and tetrahydrofuran can be used. The amount used is usually such that the resin solid content is in the range of 10 to 60%.

The resin composition obtained by the above method is applied to coated paper and heated and cured at 130 to 200°C to obtain a processed paper having a glossy surface with excellent releasability.

The process release paper using the resin composition obtained by the present invention has a higher gloss than conventional process paper, and has excellent peelability and heat resistance. It can be processed in a short time and can be expected to streamline production.

In addition, the release agent obtained by the present invention has a strong coating film and excellent repeatability, and is a new release agent composition that can be applied to everything from enamel types to matte types containing matting agents. .

Next, specific examples of the present invention will be given.

Synthesis Example 1 [Synthesis of organopolysiloxane] Both ends of the molecular chain are blocked with dimethylvinylsiloxane groups, the main chain is composed of 65 mol% of dimethylsiloxane units and 35 mol% of diphenylsiloxane units, and has a viscosity of 1900 centipoise (25 700 g of diorganopolysiloxane as a raw material (13.3 g of 2-mercaptoethanol), 2 g of benzophenone as a photoreaction accelerator, and 700 g of toluene as a reaction medium were placed in a flask, and then a 100 W high-pressure mercury lamp was inserted into the flask from above. was inserted and irradiated for 2 hours to react.

When toluene was distilled off from the reaction mixture under reduced pressure, both ends of the molecular chain of the above raw material diorganopolysiloxane were found to have the formula 705 g of a hydroxy-substituted organic group-containing diorganopolysiloxane having a viscosity of 2,500 centipoise and having a main chain having a similar structure was obtained.

Synthesis Example 2 [Synthesis of organopolysiloxane] Both ends of the molecular chain are blocked with dimethylvinylsiloxy groups, and the main chain contains 75 mol% of dimethylsiloxane units.
1000 g of a raw material diorganopolysiloxane having a viscosity of 1000 centipoise (25°C) consisting of 25 mol% of diphniel siloxane units, 16 g of 2-mercaptoethanol, 4 g of benzophenone, and 1000 g of toluene were charged into a flask, and the same procedure as in the previous example was carried out. When irradiated with light and caused to react, both ends of the molecular chain of the above raw material diorganopolysiloxane changed to the formula The main chain is converted to a structure with a similar structure and has a viscosity of 2000 centipoise (25
1005 g of a hydroxy-substituted organic group-containing diorganopolysiloxane having a temperature of 1,000 °C was obtained.

Synthesis Example 3 [Synthesis of organopolysiloxane] Both ends of the molecular chain are blocked with dimethylvinylsiloxy groups, and the main chain contains 85 mol% of dimethylsiloxane units.
800 g of a raw diorganopolysiloxane having a viscosity of 300 centipoise (25°C) consisting of 15 mol% of diphenylsiloxane units, 40 g of 2-mercaptoethanol, 5 g of benzophenone, and 800 g of toluene were charged into a flask, and the procedure was repeated in the same manner as in the previous example. When irradiated with light and caused to react, both ends of the molecular chain of the above raw material diorganopolysiloxane changed to the formula The main chain is converted to a structure with a similar structure, and the viscosity is 800 centipoise (25℃).
830 g of a hydroxy-substituted organic group-containing diorganopolysiloxane was obtained.

Synthesis Example 4 [Synthesis of silicone-modified alkyd resin] 109 parts of the hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis Example 1 (parts by weight are shown).
(same below), 172 parts of coconut oil fatty acid, phthalic anhydride
Charge 249 parts and 169 parts of glycerin into a reactor,
After reacting for about 8 hours at an internal temperature of 150 to 200°C in a nitrogen atmosphere, dilute with toluene to make the solid content 60% by weight to obtain a silicone-modified alkyd resin liquid.
Obtained 1080 copies. The physical properties were as follows.

Viscosity (Note) D Acid number 3.0 Hydroxyl number 65 (Note) Viscosity is the value determined by Gardna viscometer (25℃), the same applies hereafter.

Synthesis Example 5 [Synthesis of silicone-modified alkyd resin] 57 parts of hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis Example 2, 180 parts of coconut oil fatty acid
260 parts of phthalic anhydride and 177 parts of glycerin were charged into a reactor and reacted in the same manner as in Synthesis Example 4, followed by dilution with toluene to obtain 1040 parts of a silicone-modified alkyd resin liquid with a solid content of 60% by weight. The physical properties were as follows.

Viscosity H Acid value 2.6 Hydroxyl value 73 Synthesis example 6 [Synthesis of silicone-modified alkyd resin] 32 parts of hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis example 3, 200 parts of coconut oil fatty acid
290 parts of phthalic anhydride and 197 parts of glycerin were charged into a reactor and reacted in the same manner as in Synthesis Example 4, and diluted with toluene to obtain 1100 parts of a silicone-modified alkyd resin liquid with a solid content of 60% by weight. The physical properties were as follows.

Viscosity K Acid value 2.8 Hydroxyl value 76 Synthesis example 7 [Synthesis of silicone-modified alkyd resin] 30 parts of diorganopolysiloxane obtained in Synthesis 1,
224 parts of soybean oil fatty acid, 249 parts of phthalic anhydride, and 169 parts of glycerin were charged into a reactor and reacted in the same manner as in Synthesis Example 4. Diluted with toluene to obtain 1040 parts of a silicone-modified alkyd resin liquid with a solid content of 60% by weight. Obtained. The physical properties were as follows.

Viscosity I to J Acid value 3.5 Hydroxyl value 70 Synthesis example 8 [Synthesis of silicone-modified alkyd resin] 29 parts of hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis example 1, 232 parts of castor oil,
215 parts of phthalic anhydride and 158 parts of trimethylolpropane were charged into a reactor and reacted in the same manner as in Synthesis Example 4, and diluted with toluene to obtain 1010 parts of a silicone-modified alkyd resin liquid with a solid content of 60% by weight. The physical properties were as follows.

Viscosity Z ₃ acid value 5.8 Hydroxyl 71 Synthesis Example 9 [Synthesis of silicone-modified alkyd resin] 28 parts of hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis Example 1 and coconut oil fatty acid
172 parts were charged into a reactor and reacted for 3 hours at an internal temperature of about 180°C in a nitrogen gas atmosphere (at this time, the contents showed an acid value of 224). Further, 86 parts of ethylene glycol, 94 parts of pentaerythritol, and 249 parts of phthalic anhydride were added to this, and after reacting at 150 to 200°C for 8 hours, diluted with toluene so that the solid content was 60% by weight, the silicone 960 parts of a modified alkyd resin liquid was obtained. The physical properties were as follows.

Viscosity M Acid value 4.0 Hydroxyl value 65 Synthesis example 10 [Synthesis of silicone-modified alkyd resin] 35 parts of the hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis example 1 and the coconut oil-modified alkyd manufactured by Tokushima Essential Oil Co., Ltd. Resin (Toxinol 2420-
50) in 50% xylene (oil length 20, viscosity Z at 25°C by Gardner viscometer, acid value 15, hydroxyl number 95) was charged into a reactor, and the internal temperature was raised to 130 to 150°C in a nitrogen gas atmosphere. After reacting for about 5 hours, the mixture was diluted with toluene so that the solid content was 50% by weight to obtain 760 parts of a silicone-modified alkyd resin liquid.

Viscosity W Acid value 12.0 Hydroxyl value 82 Example 1 Silicone-modified alkyd resin liquid obtained in Synthesis Example 4
60 parts and Tesmin 350-60 [manufactured by Tokushima Essential Oil Co., Ltd., 60% isobutanol solution of butylated urea-melamine cocondensation resin] 40 parts, dryer 50 parts [manufactured by Tokushima Essential Oil Co., Ltd., 50% methanol as acid curing agent] Solution] 5 parts with solid content of 40%
It was diluted so that This varnish was coated on paper [manufactured by Kanzaki Paper Co., Ltd., mirror coated paper, 130 g/m ² ]
Coat the film to a thickness of 10μ and dry it in a hot air dryer.
A process release paper was obtained by curing at 150°C for 1 minute. The gloss at this time (manufactured by Murakami Color Research Institute, 75°) was 99%.

In addition, a one-component polyurethane solution [Krisbon 5516S, manufactured by Dainippon Ink and Chemicals Co., Ltd.] was applied on the release paper.
Coat the film to a thickness of 20μ and dry it in a hot air dryer.
It was dried at 130°C for 2 minutes and subjected to a peel force test. The peeling force at this time was 6 g/3 cm. The third peeling force after repeated use was 10 g/3 cm.

Example 2 Silicone-modified alkyd resin 60 obtained in Synthesis Example 5
40 parts and Tesmin 350-60 and 50 parts of the hair dryer
A process release paper was prepared in the same manner as in Example 1 using 5 parts of the same method as in Example 1, and the gloss and peeling force were measured in the same manner.The gloss was 100%, the peeling force was 6 g/3cm, and the peeling force on the third repeated use was 15 g. /3cm.

Example 3 Silicone-modified alkyd resin 60 obtained in Synthesis Example 6
40 parts and Tesmin 350-60 and 50 parts of the hair dryer
A process release paper was prepared in the same manner as in Example 1 using 5 parts of the same method as in Example 1, and the gloss and peeling force were measured in the same manner. It was 3cm thick.

Example 4 Silicone-modified alkyd resin 60 obtained in Synthesis Example 7
40 parts and Stemin 350-60 and 50 parts of the dryer
A process release paper was prepared in the same manner as in Example 1 using 5 parts of the same method as in Example 1, and the gloss and peeling force were measured in the same way. It was 3cm thick.

Example 5 Silicone-modified alkyd resin 60 obtained in Synthesis Example 8
40 parts and Tesmin 350-60 and 50 parts of the hair dryer
A process release paper was prepared in the same manner as in Example 1 using 5 parts of the same method as in Example 1, and the gloss and peeling force were measured in the same manner. It was 3cm thick.

Example 6 Silicone-modified alkyd resin 60 obtained in Synthesis Example 9
40 parts and Tesmin 350-60, 5 parts of hair dryer 50
A process release paper was prepared in the same manner as in Example 1, and the gloss and peeling force were measured in the same manner. It was hot.

Example 7 Silicone-modified alkyd resin 72 obtained in Synthesis Example 10
40 parts and Tesmin 350-60, 5 parts of hair dryer 50
A process release paper was prepared in the same manner as in Example 1, and the gloss and peeling force were measured in the same manner. It was hot.

Example 8 Silicone-modified alkyd resin 60 obtained in Synthesis Example 7
A process release paper was prepared in the same manner as in Example 1 using 48 parts of Tesmin ME50L (50% n-butanol solution of butylated melamine resin manufactured by Tokushima Essential Oils Co., Ltd.) and 10 parts of dryer 50. When the gloss and peeling force were measured, the gloss was 101%, the peeling force was 20 g/3 cm, and the peeling force after repeated use was 35 g/3 cm.

Example 9 Silicone-modified alkyto resin 30 obtained in Synthesis Example 4
30 parts of Toxinol 2411-60 [manufactured by Tokushima Essential Oil Co., Ltd., coconut oil-modified alkyd resin, oil length 33, 60% xylene solution], 48 parts of Tesmin ME50L, and 50 parts of a dryer.
A process release paper was prepared in the same manner as in Example 1 using 10 parts of the same, and the gloss and peeling force were measured in the same manner.The gloss was 101%, the peeling force was 8 g/3cm, and the peeling force on the third repeated use was 15 g/3cm. It was 3cm thick.

Example 10 Silicone-modified alkyd resin 96 obtained in Synthesis Example 10
A process release paper was prepared in the same manner as in Example 1, using 15 parts of Tesmin 201-80 (80% n-butanol solution of methylated melamine resin, manufactured by Tokushima Essential Oil Co., Ltd.) and 10 parts of Dryer 50. When the gloss and peeling force were similarly measured, the gloss was 102%, the peeling force was 6 g/3 cm, and the peeling force after repeated use was 8 g/3 cm.

Example 11 Silicone-modified alkyd resin 10 obtained in Synthesis Example 4
20 parts of Toxinol 2411-60, Tetroid
795 [Made by Tokushima Essential Oils Co., Ltd., acrylic resin, viscosity R, acid value
7.0, hydroxyl number 72, 60% xylene solution〕30
part, 48 parts of Tesmin ME50L, 10 parts of dryer 50
A process release paper was prepared in the same manner as in Example 1, and the gloss and peeling force were measured in the same manner. It was hot.

Example 12 Silicone-modified alkyd resin 24 obtained in Synthesis Example 10
20 parts of Toxinol 2411-60, Tetroid
20 parts of 795, 48 parts of Tesmin ME50L, hair dryer
A process release paper was prepared using 10 parts of 50 in the same manner as in Example 1, and the gloss and peeling force were measured in the same way.The gloss was 100%, the peeling force was 18 g/3cm, and the peeling force for the third repeated use was 35 g. /3cm, it was hot.

Example 13 Silicone-modified alkyd resin 40 obtained in Synthesis Example 5
A process release paper was prepared in the same manner as in Example 1, using 40 parts of Tesroid 795, 15 parts of Tesmin 201-80 (manufactured by Tokushima Essential Oil Co., Ltd., methylated melamine resin), and 10 parts of Dryer 50. When the gloss and peeling force were measured, the gloss was 101%, the peeling force was 7 g/3 cm, and the peeling force after repeated use was 10 g/3 cm.

Synthesis Example 11 [Synthesis of silicone-modified acrylic resin] 40 parts of the hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis Example 1 and 304 parts of xylene were charged into a reactor, and the internal temperature was raised to 125% under nitrogen gas atmosphere.
The temperature was raised to ~130°C, and the following mixed solution was added dropwise at a constant rate over a period of 3 hours.

Methacrylic acid 40 parts Methyl methacrylate 80 Butyl methacrylate 200 Styrene 40 2-hydroxyethyl acrylate 40 α, α′-Azobisisobutyronitrile 11 Di-t-butyl peroxide 2 After completion of the dropwise addition, react at the same temperature for 5 hours. Subsequently, 755 parts of silicone-modified acrylic resin liquid was obtained.

Solid content 60.5% Viscosity N Hydroxyl number 25 Synthesis example 12 [Synthesis of silicone-modified acrylic resin] 40 parts of the hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis Example 3 and 304 parts of xylene were charged into a reactor, and synthesis was carried out. The following mixed solution was added dropwise in the same manner as in Example 11.

Acrylic acid 40 parts Methyl methacrylate 120 Butyl acrylate 200 2-hydroxyethyl acrylate 40 α,α′-azobisisobutyronitrile 11 Di-t-butyl peroxide 2 After the dropwise addition, the reaction was continued at the same temperature for 5 hours. Solid content 60% Viscosity L Hydroxyl value 25 Synthesis example 13 [Synthesis of silicone modified acrylic resin] 42 parts of hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis example 1 755 parts of silicone-modified acrylic resin liquid obtained and Tesroid 795
700 parts of the mixture was charged into a reactor, the internal temperature was raised to 130 to 180°C in a nitrogen gas atmosphere, and the mixture was reacted for about 5 hours to obtain 742 parts of a silicone-modified acrylic resin. This was diluted with xylene so that the solid content was 60%.

Viscosity 0 Acid value 6.3 Hydroxyl value 66 Example 14 Silicone-modified alkyd resin liquid obtained in Synthesis Example 4
30 parts, 30 parts of silicone-modified acrylic resin liquid obtained in Synthesis Example 11, 40 parts of Tesmin 350-60, dryer
50 was used to prepare a process release paper in the same manner as in Example 1, and the gloss and peeling force were measured in the same manner.The gloss was 94%, the peeling force was 6 g/3cm, and the peeling force for the third repeated use was 10 g. /3cm.

Example 15 Silicone-modified alkyd resin liquid obtained in Synthesis Example 7
30 parts, 30 parts of silicone-modified acrylic resin liquid obtained in Synthesis Example 12, 40 parts of Tesmin 350-60, dryer
50 was used to prepare a process release paper in the same manner as in Example 1, and the gloss and peeling force were measured in the same manner.The gloss was 98%, the peeling force was 7 g/3cm, and the peeling force for the third repeated use was 10 g. /3cm.

Example 16 Silicone-modified alkyd resin liquid obtained in Synthesis Example 8
30 parts, 30 parts of silicone-modified acrylic resin liquid obtained in Synthesis Example 13, 40 parts of Tesmin 350-50, dryer
A process release paper was prepared using 5 parts of 50 in the same manner as in Example 1, and the gloss and peeling force were measured in the same manner.The gloss was 97%, the peeling force was 6 g/3cm, and the peeling force for the third repeated use was 10 g. /3cm.

Example 17 Silicone-modified alkyd resin liquid obtained in Synthesis Example 10
36 parts, 30 parts of silicone-modified acrylic resin liquid obtained in Synthesis Example 13, 48 parts of Tesmin ME50L, dryer
A process release paper was prepared using 10 copies of 50 in the same manner as in Example 1, and the gloss and peeling force were measured in the same manner.The gloss was 100%, the peeling force was 6 g/3cm, and the peeling force for the third repeated use was 10 g. /3cm.

Comparative example 1 Process paper release agent Tespiel Sp2400G [Tokushima essential oil
Co., Ltd., by blending 5 parts of Dryer 50 with 100 parts of glossy amino alkyd resin] to prepare process release paper in the same manner as in Example 1. When the gloss and peeling force were similarly measured, the gloss was 98. %, peeling force was 220 g/3 cm, and peeling force at the third repeated use was 300 g/3 cm or more.

Comparative example 2 Release agent for process paper Toxinol 2400Y [Tokushima essential oil
Co., Ltd., coconut oil modified alkyd resin, oil length 40%, 60%
A process release paper was prepared using 100 parts of toluene solution and 55 parts of Desmodil L in the same manner as in Example 1, and the gloss and peeling force were measured in the same way.The gloss was 103%, the peeling force was 300g/3cm or more, and the result was 3rd time of repeated use. The peeling force was 300 g/3 cm or more.

Claims (1)

[Claims] 1 (a) General formula [Here, Me is a methyl group, Ph is a phenyl group,
m and n are positive integers, m+n is 30 to 1000, and R ¹ represents an organic group, at least one of which has the formula
HO―R―(S) ₂ -R― (here R is 1 carbon number
~10 divalent hydrocarbon groups, a is 0 or 1), and 15 to 50 mol% of the organic groups bonded to silicon atoms are phenyl groups. Silicone-modified alkyd resin modified with siloxane
100 parts by weight, (b) Alkanol-modified amino resin
15 to 150 parts by weight; and (c) 1 to 20 parts by weight of an acidic catalyst.