JP2000095929A - Release agent composition for process release paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a release agent for synthetic leather process paper which has an especially good release property, gloss, surface state and repetitive usability and is dry hard at a temperature substantially lower than was previously required at peel ply formation. SOLUTION: In a release agent composition for process release paper comprising an alkyd resin (A), an amino resin (B) and a silicone resin (C) containing a functional group having a reactivity against these resins, the amino resin contains a methylated melamine resin containing one or more methylol group per triazine nucleus as a main component. Furthermore, the solid component weight ratio of the alkyd resin (A) to the amino resin (A/B) is within the range of from 90/10 to 40/60, and the solid component weight ratio of the silicone resin (C), which contains a functional group having a reactivity against these resins, to 100 pts.wt. total of these resins ((A+B)/C) is within the range of from 100/1 to 100/20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a release agent composition for a process release paper, and more particularly, to a process release paper having excellent releasability at high temperature, excellent gloss, surface condition and repetitive use. The present invention relates to a release agent composition that can be cured and dried at a lower temperature than before and is suitable for energy saving and cost saving.

[0002]

2. Description of the Related Art Conventionally, production of synthetic leather and the like has been performed by a casting method of urethane resin, vinyl chloride resin, polyamide resin, amino acid resin, etc. In this production, the surface of process paper is peeled (peeled). ), A release agent composition for process release paper is used. As a release agent composition for this step release paper, a polypropylene-based release agent composition,
Amino alkyd-based, silicone-based resin compositions are known as typical ones, but polypropylene-based ones are difficult to use at high temperatures and the peeled surface is easily damaged, and amino alkyd-based ones are poorly peeled, Silicones have the disadvantage of poor gloss, and all are said to have advantages and disadvantages.

[0003] Further, as a release agent composition for this step release paper, an alkyd resin or an acrylic resin is modified with an organopolysiloxane having a hydroxyl group, and thermally cured using a crosslinking agent (Patent Nos. 2733417 and 1219).
049, no. No. 1156343, no. 134820
0, Japanese Patent Publication No. 7-53820).

[0004] Release paper coated with these compositions is excellent in gloss, release property and surface condition and has sufficient properties for producing synthetic leather. However, as synthetic leather is repeatedly produced, Since the peeling force gradually decreases and eventually does not peel off, there is a problem that the production efficiency is poor. Also,
When these compositions are applied to form a release layer, 150
It requires a curing and drying temperature of at least ℃, and there is a problem that the heat reduces the feel of the release paper and increases energy consumption.

[0005]

As described above, in the prior art as described above, the usable life of the process paper is small and the performance is not sufficiently satisfied at present. There was also a strong demand for a temperature decrease during curing and drying.

That is, the present invention provides gloss, peeling force, surface condition,
It is another object of the present invention to provide a release agent composition for a process release paper which has excellent repetitive usability and can be cured and dried at a low temperature to form a release layer.

[0007]

In the production of synthetic leather, the process paper not only plays a role of forming the surface of the synthetic leather, but also, for example, firstly, a urethane resin of one liquid is applied to the process paper, dried, and then dried. After applying a two-part urethane resin as an adhesive from above, further laminating the base fabric and aging, these series of steps in which the synthetic leather is finally peeled off from the process paper are repeated, so it is very severe Must withstand use conditions.

The inventors of the present invention have made intensive studies in consideration of the use conditions of the process release paper and the above object, and have found that the release paper made of an alkyd resin, an amino resin, and a methylphenyl silicone resin containing a reactive functional group is used. In the agent composition, the amino resin contains a methylated melamine resin having one or more methylol groups per triazine nucleus as a main component, so that the methylol groups are involved in both self-condensation and crosslinking reactions. Amino group, a curing agent, causes a cross-linking reaction with the alkyd resin, which is the main component, and the methylphenyl silicone resin, which contains a functional group. A release coating film with excellent heat resistance was formed under drying conditions at lower temperatures. Compared to paper, peel strength, gloss, surface state equal or, it was confirmed that reduction of the release of the repeated use is small.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a release agent composition comprising an alkyd resin, an amino resin, and a silicone resin containing a functional group reactive with these resins, wherein the amino resin has a methylol group and a triazine nucleus. The present invention relates to a release agent composition for a process release paper, which comprises as a main component at least one methylated melamine resin.

The alkyd resin constituting the composition of the present invention may be a known one. However, this alkyd resin has an oil length of 0 to 60, preferably 20 to 40, an acid value of 1 to 30, preferably 5 to 25, and a hydroxyl value of 50 to 300, preferably 100 to 250. It is desirable to use soybean oil or soybean oil fatty acid, castor oil, castor oil fatty acid and the like. In addition, these alkyd resins include acrylic resin, polyester resin,
It is also possible to use a modified or mixed epoxy resin, phenol resin or the like.

The amino resin constituting the composition of the present invention must contain, as a main component, a methylated melamine resin containing at least one methylol group per triazine nucleus. If the proportion of the methylated melamine resin in the amino resin is small, the effects of the present invention cannot be achieved. It is desirable that the ratio be approximately 50% by mass or more. In addition, other amino resins, for example, other methylated melamine resins, butylated melamine resins, methylated urea resins,
Butylated urea resin, methylated benzoguanamine resin, butylated benzoguanamine resin, etc.
It is possible to use them together within a range not exceeding mass%.

In the present invention, the methylated melamine resin having a methylol group must have at least one methylol group per triazine nucleus. When the number of methylol groups is less than one, the crosslinking density of the release layer is low, so that the deterioration progresses rapidly after repeated use, and the life of the process paper is shortened. In addition, since the curability is low, it is necessary to obtain 1
A high drying temperature of 50 ° C. or higher is required, and the effects of the present invention cannot be achieved.

The methylated melamine resin can be obtained usually by adding formalin to melamine under basic conditions and then etherifying methanol under acidic conditions. Depending on the difference, the amounts of imino group, methylol group, and methyl ether group, which are functional groups of the amino resin, can be controlled. The amount of methylol group per triazine nucleus is a value calculated from titration analysis and instrumental analysis.

In the present invention, the ratio (A / B) of the alkyd resin (A) and the amino resin (B) is 9
A ratio of 0/10 to 40/60 is preferred. Within this range, all of the gloss, the peeling power, and the repetitive usability can be satisfied. When the ratio is 90/10 or more, a sufficient crosslinked structure cannot be obtained in the release layer, and a reduction in the release force and a reduction in the number of times of repeated use occur. On the other hand, when the ratio is 40/60 or less, the release layer tends to be hard and brittle, and the release tends to be difficult.

The silicone resin constituting the composition of the present invention must contain a functional group reactive with the above-mentioned alkyd resin and / or amino resin. This is because the alkyd resin and amino resin forming the release layer and the present silicone resin, which is a release component, have a structure chemically bonded in the release layer, so that the transfer of silicone to the synthetic leather layer during the production of synthetic leather. Can be suppressed, and it can be used repeatedly. As its functional group,
Those having reactivity with an alkyd resin and / or an amino resin such as a hydroxyl group, an amino group, a carboxyl group, and a glycidyl group may be mentioned, and it is preferable that at least one is contained in one molecule. The functional group having reactivity with the alkyd resin and / or the amino resin is preferably a hydroxyl group, and 1 to 10 per molecule of the silicone resin.
It is better to contain them individually. This silicone resin is excellent in heat resistance, has good gloss, and is linear as long as the object of the present invention of obtaining a process release paper with good releasability is achieved. Any of a branched chain structure may be used, but it is preferable to have excellent compatibility with the above-mentioned alkyd resin and amino resin.

The silicone resin gives the release agent composition for process paper of the present invention an excellent release property, glossiness, repetitive use property, and wettability with a urethane resin which is a surface layer of synthetic leather. It is preferable that 10 to 50 mol% of the silicon-bonded organic groups in one molecule of the silicone resin is a phenyl group, more preferably 15 to 40%.

In the present invention, the ratio ((A + B) / (C)) of the alkyd resin (A) and the amino resin (B) to the silicone resin (C) is 100 in terms of solid content mass ratio.
/ 1 to 100/20 is desirable. Within this range, all of the peeling force, gloss, and surface state can be satisfied. When the ratio is less than 100/1, a sufficient peeling force may not be obtained. On the other hand, when the ratio is more than 100/10, the curability may decrease, and the transfer of the silicone resin and the decrease in gloss may occur.

In the present invention, an acidic catalyst can be used at the time of curing and drying. For this, known compounds such as p-toluenesulfonic acid and hydrochloric acid which are usually used as a curing catalyst when a alkyd resin and an amino resin undergo a crosslinking reaction can be used.

In the present invention, the release agent composition for the process release paper can be obtained by mixing or reacting a predetermined amount of each component described above. In addition, this resin composition is usually used as an organic solvent solution for convenience in use, and as the organic solvent, a conventionally known organic solvent having good solubility with each component and having no reactivity is used. Can be used. For example, toluene, xylene, methanol, ethanol, isobutanol, n-butanol, methyl ethyl ketone, acetone, tetrahydrofuran or the like or a mixture of two or more thereof can be used. It is desirable to be within the range. It should be noted that the resin composition may be a mat type by blending a conventionally known matting agent.

[0020]

EXAMPLES The present invention will be specifically described below with reference to preferred examples, but the present invention is not limited to these examples. Further, "parts" and "%" shown in Examples are parts by mass and% by mass unless otherwise specified. The performance evaluation of the process release paper was performed according to the following method.

1) Gloss: Gloss at an angle of 60 ° was measured using a gloss needle GM-3D (manufactured by Murakami Color Research Laboratory Co., Ltd.).

2) Initial release force: A one-pack type polyurethane solution Chrisbon 5516S (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) is applied on the prepared release paper so that the film thickness becomes 20 μm, and dried with hot air. After drying in an oven at 130 ° C. for 2 minutes, the peeling force was measured with a width of 3 cm.

3) Third peeling force: A one-pack type polyurethane solution Chrisbon 5516S (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) is applied on the prepared release paper so that the film thickness becomes 20 μm, and hot air is applied. 130 ° C x 2 in a dryer
And heat-treated at 140 ° C. for 10 minutes and peeled off. This operation was repeated three times, and the third peeling force was measured with a width of 3 cm.

4) Repeatability: One-component polyurethane solution Chrisbon 5516S (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) is applied on the prepared release paper so that the film thickness becomes 20 μm, and dried with hot air. 130 ° C x 2 in the vessel
And heat-treated at 140 ° C. for 10 minutes and peeled off. This operation was repeated until the peeling layer was removed and the film could not be peeled off, and the number of times of use was repeated.

5) Surface condition: The presence or absence of cissing and unevenness on the surface of the release layer were visually evaluated.

Example 1 Palm oil-modified alkyd resin Tesluck 2052-60 (trade name, manufactured by Hitachi Chemical Co., Ltd.) 60 parts, hydroxyl group-containing methylphenyl silicone K
NS902 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts, methylated melamine resin Cymer 350 (trade name, Mitsui Cytec Co., Ltd., methylol group content: 1.1 / triazine nucleus) 35
And 5 parts of a 50% methanol solution of paratoluenesulfonic acid were added thereto, and the mixture was diluted with toluene to give a solid content of 4 parts.
0% was obtained to obtain a process release agent. Next, this solution was coated on a mirror-coated paper (coated paper manufactured by Oji Paper Co., Ltd., basis weight 130 g / m ² ) so that the film thickness became 10 μm, and then heated in a hot air dryer at 130 ° C. for 1 minute at 150 ° C. ° C
It was cured under each of the conditions for one minute to produce a process release paper.

Example 2 Castor oil-modified alkyd resin Teslac 2002-60 (trade name, manufactured by Hitachi Chemical Co., Ltd.) 65 parts, methylphenyl silicone KNS90
2 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts, methylated melamine resin Cymel 350 (trade name, Mitsui Cytec Co., Ltd., methylol group content: 1.1 / triazine nucleus) 20 parts, butylated urea melamine resin Tesazine 3103 -10 (manufactured by Hitachi Chemical Co., Ltd.) and 5 parts of a 50% methanol solution of p-toluenesulfonic acid were added, and the mixture was diluted with toluene and blended to have a solid content of 40%.
A process release agent was obtained. Next, a process release paper was produced in the same manner as in Example 1.

Comparative Example 1 Process release paper was prepared in the same manner as in Example 1 except that the amino resin of Example 1 was changed to a butylated urea melamine resin Tesazine 3103-60 (trade name, manufactured by Hitachi Chemical Co., Ltd.). Was prepared.

Comparative Example 2 The amino resin of Example 1 was butylated with a melamine benzoguanamine resin, Tesazine 3027.
A process release paper was prepared in the same manner as in Example 1 except that the product was changed to -60 (trade name, manufactured by Hitachi Chemical Co., Ltd.).

Comparative Example 3 The procedure of Example 1 was repeated except that the amino resin of Example 1 was changed to methylated melamine resin Cymel 303 (trade name of methylol group, manufactured by Mitsui Cytec Co., Ltd .: 0.3 per triazine nucleus). A process release paper was produced in the same manner as in Example 1.

130 ° C. of Examples 1-2 and Comparative Examples 1-3
Table 1 shows the results of the evaluation when dried for 1 minute and Table 2 shows the results of the evaluation when dried for 1 minute at 150 ° C.

[0032]

[Table 1]

[0033]

[Table 2]

From these tables, it can be seen that the release agent composition for process release paper of the present invention is used at 130 ° C. × 1 minute drying condition, which is 20 ° C. lower than the conventionally used 150 ° C. × 1 minute drying condition. It can be seen that the obtained process release paper has good gloss, release force, surface condition, and excellent repetitive usability.

[0035]

By adopting the constitution of the present invention, the gloss, the peeling force and the surface condition are particularly excellent, and it is possible to cure and dry at a significantly lower temperature than before, and even at this temperature, it is possible to use repeatedly. , An extremely remarkable effect of obtaining a release agent composition for a process release paper having an increased value can be provided.

Claims (3)

[Claims] 1. A release agent composition comprising an alkyd resin (A), an amino resin (B), and a silicone resin (C) having a functional group reactive with these resins,
A release agent composition for a process release paper, wherein the amino resin contains a methylated melamine resin containing at least one methylol group per triazine nucleus as a main component. 2. The ratio of the alkyd resin (A) to the amino resin (A / B) is in the range of 90/10 to 40/60 in terms of solid mass ratio, and the total amount is 100 parts by mass. The process according to claim 1, wherein the ratio ((A + B) / C) of the silicone resin (C) having a functional group reactive with the resin is in the range of 100/1 to 100/20 in terms of solid content mass ratio. Release agent composition for release paper. 3. The functional group-containing silicone resin is characterized in that 15 to 50 mol% of the silicon atom-bonded organic groups in one molecule are phenyl groups, and at least one of the remaining organic groups has reactivity with the amino resin. The release agent composition for a process release paper according to claim 1, which is an organopolysiloxane that is a functional group-substituted organic group.