JPH0672213B2 - Process release paper resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention provides a resin composition for process release paper, particularly excellent releasability and gloss at high temperature, which does not cause silicone stains, and The present invention relates to a resin composition for process release paper used in manufacturing.

(Prior Art) Conventionally, as a resin composition for imparting releasability (releasability) to the surface of process paper, three types of polypropylene, aminoalkyd resin, and silicone have been known as typical ones. ing.

However, these have merits and demerits, and polypropylene-based ones are excellent in endurance of peelability when repeatedly used, but have limitations in use at relatively high temperature,
In this case, the peeled surface is easily scratched, and the enamel (strong gloss) type product (synthetic leather etc.) cannot be obtained. On the other hand, the aminoalkyd resin type has excellent gloss. It has poor releasability, and although silicone-based ones are excellent in releasability, they have drawbacks such as being unsuitable for enamel type synthetic leather due to poor gloss.

Therefore, the present applicants previously noted that 15 to 50 mol% of all organic groups bonded to a silicon atom are phenyl groups, and other organic groups are HO-R- (S) a-R- (here Where R is a divalent hydrocarbon group and a is 0 or 1) is a composition comprising a silicone-modified alkyd resin or silicone-modified acrylic resin modified with an organopolysiloxane which is a hydroxy-substituted organic group, and a polyisocyanate compound. Kosho 58
No. 53680, Japanese Patent Publication No. 57-48013), and a composition obtained by adding an alkanol-modified amino resin and an acid catalyst to the silicone-modified alkyd resin or silicone-modified acrylic resin (Japanese Patent Publication Nos. 63-32825 and 61-61). 13507).

(Problems to be Solved by the Invention) However, although all of these compositions have excellent releasability at high temperatures and give good gloss, the silicone-modified alkyd resin and silicone-modified acrylic resin are organopolysiloxanes. difficult to obtain those constant quality for easy content of hydroxy-substituted organic group described above varies during synthesis in the medium, the hydroxy substituted organic groups in order to overcome this drawback -CH ₂ CH ₂ CH ₂ If it is represented by --OC ₂ H ₄ OmH (m = 0 to 3), a large amount of impurities that do not contain this group are produced, and thus there is a drawback that silicone stains are likely to occur.

(Means for Solving the Problems) The present invention relates to a resin composition for process release paper, which solves the above disadvantages and drawbacks. (A) Alkyd resin or acrylic resin 99 to 70 parts by weight, ) 9.4 mol% or more of the organic groups bonded to silicon atoms in one molecule are of the formula (Wherein R ¹ is a hydrogen atom, a methyl group or an ethyl group, and n is 0 to 5) is a phenyl group-substituted alkyl group,
At least one of the remaining organic groups is an organopolysiloxane having a hydroxy group-substituted alkyl group represented by the formula —CH ₂ —CH ₂ —CH ₂ —OC ₂ H ₄ OmH (where m = 0 to 3). 30 parts by weight, (c) 15 to 150 parts by weight of an alkanol-modified amino resin, and (d) 1 to 20 parts by weight of an acidic catalyst.

That is, as a result of various studies to develop a resin composition for process release paper which does not involve the above-mentioned disadvantages, the present inventors have found that the above silicone-modified alkyd resin, silicone-modified acrylic resin is replaced with an alkyd resin or an acrylic resin. And an organopolysiloxane containing a phenyl group-substituted alkyl group and a hydroxy-substituted alkyl group, and an alkanol-modified amino resin and an acidic catalyst are added to the organopolysiloxane, a process exfoliation using a conventionally known resin composition is performed. It was found that a resin composition for process release paper, which has better gloss, better releasability and heat resistance than paper, and does not cause silicone stain, can be obtained, and about the constitution of the organopolysiloxane used here. To complete the present invention.

(Function) As described above, the resin composition for step release paper of the present invention is (a) alkyd resin or acryl resin, and (b) 9.4 to 49.8 mol% of organic groups bonded to silicon atoms in one molecule.
An organopolysiloxane in which is a phenyl-substituted alkyl group and the other organic group is a hydroxy-substituted alkyl group,
(C) An alkanol-modified amino resin and (d) an acidic catalyst.

The alkyd resin and acrylic resin used as the component (a) may be conventionally known ones. Therefore, this alkyd resin may be prepared by a usual synthetic reaction, that is, by reacting a polyhydric alcohol with a fatty acid, a polybasic acid or the like, which is a glycol such as ethylene glycol, diethylene glycol, propylene glycol or neopentyl glycol. Glycerin, trimethylolpropane, trimethylolethane, polyhydric alcohols such as pentaerythritol and octylic acid, lauric acid, saturated fatty acids such as palmitic acid, coconut oil, coconut oil fatty acid, castor oil, castor oil fatty acid, soybean oil, Unsaturated oils such as soybean oil fatty acids and fatty acids such as unsaturated oil fatty acids, polybasic acids such as phthalic anhydride, isophthalic acid, adipic acid, maleic anhydride, fumaric acid, trimellitic anhydride, etc. Mix at a specified ratio and heat the condensation reaction. The fatty acid used here has an oil length of 0 to 60, preferably 20 to 40, from the viewpoints of peelability and coating performance. The reaction ratio of alcohol with fatty acid and polybasic acid is OH / COOH equivalent is 1.0
˜1.6, preferably 1.2 to 1.4.

Further, since this acrylic resin may be one produced by a known method, it may be one obtained by solution polymerization, suspension polymerization or emulsion polymerization of an acrylic monomer.

Next, in the organopolysiloxane as the component (b) constituting the composition of the present invention, 9.4 to 49.8 mol% of the organic group bonded to the silicon atom in one molecule is represented by the formula. And R ¹ is a hydrogen atom, a methyl group or an ethyl group, n
= 0 to 5 is a phenyl group-substituted alkyl group, and at least one of the remaining organic groups is represented by the formula: —CH ₂ —CH ₂ —CH ₂ —OC ₂ H ₄ OmH (2) , M is a hydroxy group-substituted alkyl group of 0 to 3, and the remaining organic groups are alkyl groups such as methyl group, ethyl group, propyl group, butyl group, octyl group, vinyl group, and the like. , An alkenyl group such as an allyl group, an aryl group such as a phenyl group, a tolyl group, or a chloromethyl group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, a cyano group, a trifluoropropyl group, or cyanoethyl It may be an unsubstituted or substituted monovalent hydrocarbon selected from groups and the like, but it is preferably a methyl group.

The molecular structure of this organopolysiloxane is such that it imparts heat resistance and good gloss to the composition of the present invention, and excellent releasability, so that if it imparts these physical properties, a linear chain structure is obtained. Although it may have a branched structure or a branched structure, it is desirable that it has excellent compatibility with the alkyd resin and acrylic resin as the above-mentioned component (a). Therefore, the preferred organopolysiloxane is of the formula And R ² is a phenyl group-substituted alkyl group represented by the above formula (1), R ³ is an organic group, at least one of which is a hydroxy group substituted alkyl group represented by the above formula (2), and l + k is 5 to 1,000 and 0.15 for l / 2 (l + k)
In the following, cissing will increase, and if it is 0.5 or more, the synthesis itself will be difficult, so it is set to 0.15 to 0.5, but the content of the phenyl group-substituted alkyl group in this organopolysiloxane is less than 9.4 mol%. Therefore, it is necessary to make it 9.4 mol% or more, and at least one of the remaining organic groups is represented by the above formula (2).
The reason why the hydroxy group-substituted alkyl group represented by the formula (3) is used is that, unless such an organopolysiloxane is used, releasability, glossiness, and repellency when used for synthetic leather are not satisfied.

In addition, such an organopolysiloxane is an organohydrogenpolysiloxane containing a hydrogen atom bonded to a silicon atom, which is used as a phenyl group-substituted alkyl group-containing compound represented by the formula (1). Adding a predetermined amount of _{CH 2 = CH-CH 2 -O} (C 2 H 4 O) mH as hydroxyl group-substituted alkyl group-containing compound represented by preparative formula (2), platinum-based, such as chloroplatinic acid It can be obtained by subjecting these to an addition reaction using a catalyst. According to this, the phenyl group-substituted alkyl group represented by the formula (1) and the hydroxy group-substituted alkyl group represented by the formula (2) are contained. Since it contains a small amount of fluctuation, it is possible to easily obtain organopolysiloxane with stable quality, and this organopolysiloxane needs to be modified beforehand by cooking the alkyd resin or acrylic resin. However, this composition can be used as a resin composition for process release paper having excellent physical properties only by cold blending.

Further, as the alkanol-modified amino resin as the component (c) constituting the composition of the present invention, any of those generally commercially available can be used, including methoxymethyl roll melamine resin and butoxy. Examples include methylol melamine resin, butoxy methylol urea-melamine co-condensation resin, butoxy methylol benzoguanamine resin.

The acidic catalyst as the component (d) constituting the composition of the present invention may be any one of paratoluenesulfonic acid, hydrochloric acid and the like which are usually used in aminoalkyd resins.

The resin composition for process release paper of the present invention is prepared by mixing the above-mentioned (a) alkyd resin or acrylic resin, (b) organopolysiloxane, (c) alkanol-modified amino resin and (d) an acidic catalyst in a predetermined amount. Although it can be obtained, when the amount of the organopolysiloxane is less than 1 part by weight in 100 parts by weight of the mixture of the alkyd resin or acrylic resin as the component (a) and the organopolysiloxane as the component (b), If the amount exceeds 30 parts by weight, the compatibility becomes poor. Therefore, this is because 1 to 100 parts by weight of the alkyd resin or acrylic resin as the component (a), 1 to 2 parts of the organopolysiloxane as the component (b). It should be 30 parts by weight. In addition, a mixture 100 of this (a) component and (b) component
If the amount of the alkanol-modified amino resin as the component (c) is less than 15 parts by weight, the gloss becomes poor, and if it is more than 150 parts by weight, peeling failure occurs.
The amount of the acid catalyst as the component (d) is less than 1 part by weight per 100 parts by weight of the mixture of the component (a) and the component (b), and the curing will be poor. If the amount is more than the weight part, peeling failure will occur, so the amount may be 1 to 20 parts by weight. In addition, this (a), (b), (c),
(D) If the compounding ratio of each component deviates from these ranges, the above-mentioned preferable physical properties cannot be obtained, so that it is necessary to set this range, and if necessary, known silicone-modified alkyd resin may be used. It is optional to add a silicone-modified acrylic resin.

It is convenient for the resin composition of the present invention to be used as a solvent solution, and the solvent used for this purpose has no reactivity with the components (a) and (b). Since it is sufficient, one or a mixture of two or more of benzene, toluene, xylene, methanol, ethanol, isobutanol, normal butanol, methyl ethyl ketone, acetone, tetrahydrofuran, etc. is exemplified as the amount used. In general, the resin solid content may be in the range of 10 to 60%.

The resin composition obtained by the above method is applied to coated paper and cured by heating at 130 to 200 ° C. to give a process paper having a glossy surface excellent in peelability. Compared to conventional process paper, the process release paper has better gloss, does not generate silicone stains, and has excellent releasability and heat resistance. This is also the case when manufacturing synthetic leather. Since high temperature and short time processing is possible, rationalization in production can be expected.

Further, since the resin composition for release paper of the present invention has a strong coating film and excellent repeatability, a new release agent composition applicable to all types from enamel type to matte type containing a matting agent. Is.

(Example) Next, a synthetic example of the organopolysiloxane used in the production of the resin composition for step release paper of the present invention and an example of the present invention will be described. In the examples, parts are parts by weight and viscosity is 25 It shows the measured values at ° C.

Synthesis Example 1 Both ends of the molecular chain are blocked with trimethylsilyl groups,
The following formula containing a hydrogen atom bonded to a silicon atom in the molecule 160.9 g of methylhydrogenpolysiloxane represented by
A mixture of 195.9 g of α-methylstyrene and 0.01 g of chloroplatinic acid was added dropwise at 80 ° C., and after completion of the reaction, the mixture was reacted at 120 ° C. for 8 hours, and then 9.9 g of allyl glycol and chloroplatinic acid of 0.
After dropping the mixture with 001g, react at 80-120 ℃ for 8 hours,
Then, the reaction product was treated by a conventional method, and 65.3 mol% of all organic groups bonded to the silicon atom were methyl groups, and 3
2.8 mol% is a phenyl-substituted alkyl group and has a viscosity of 1
320 g of a transparent organopolysiloxane (abbreviated as siloxane A hereinafter) having 0.100 cp was obtained. Since this product has a hydroxyl value of 7.8 KOHmg / g, it contains two hydroxyl groups in one molecule. It was confirmed.

Synthesis Example 2 Both ends of the molecular chain are blocked with trimethylsilyl groups,
The following formula containing a hydrogen atom bonded to a silicon atom in the molecule 192.5 g of methylhydrogen polysiloxane represented by
, Α-methylstyrene 212.4g and allyl glycol 10.2
When g and g were dropped and reacted in the same manner as in Synthesis Example 1, 65.5 mol% of the organic groups bonded to the silicon atom were methyl groups, 32.7 mol% were phenyl group-substituted alkyl groups, and Since the valence is 13.5 KOHmg / g, there are about two hydroxyl groups in one molecule, and the viscosity is 4,850 cp.
380 g of organopolysiloxane (hereinafter abbreviated as siloxane B) was obtained.

Synthesis Example 3 Both ends of the molecular chain are blocked with trimethylsilyl groups,
The following formula containing a hydrogen atom bonded to a silicon atom in the molecule 156.2g of methylhydrogen polysiloxane
, 123.5 g of α-methylstyrene and 11.8 g of allyl glycol
When g and g were dropped and reacted in the same manner as in Synthesis Example 1, 75.6 mol% of the organic group bonded to the silicon atom was a methyl group, 21.9 mol% was a phenyl group-substituted alkyl group, and a hydroxyl group. The value is 20.4KOH mg / g, so there are about 2 hydroxyl groups in one molecule, and the viscosity is 1,890cp.
270 g of organopolysiloxane (hereinafter abbreviated as siloxane C) was obtained.

Synthesis Example 4 172.7 g of α-methylstyrene in Synthesis Example 1
Was treated in the same manner as in Synthesis Example 1, except that 65.3 mol% of the organic groups bonded to the silicon atom were methyl groups and 3
2.8 mol% is a phenyl group-substituted alkyl group, and since the hydroxyl value is 8.3 KOHmg / g, there are about two hydroxyl groups in one molecule, and the organopolysiloxane has a viscosity of 10,620 cp (hereinafter referred to as siloxane). Abbreviated as D) 305g
was gotten.

Example 1 32.5 parts of coconut oil modified alkyd resin, 1.5 parts of siloxane A,
7.5 parts of methylated melamine resin and 10 parts of butylated urea melamine resin were mixed and diluted with 40.5 parts of toluene and 8 parts of isobutanol, and then 2 parts of 50% paratoluenesulfonic acid-methanol solution was added and mixed well. Then, a resin composition was prepared.

Then, this composition was applied to Miracoat paper (trade name, manufactured by Kanzaki Paper Co., Ltd.) of 130 g / m ² of tsubo so that the coating film would be 10 M, and heated in a hot air dryer at 150 ° C. for 1 minute to cure. The process release paper was made to have a gloss of 102 gloss (20 ° C).

Next, this release paper was coated with a one-component polyurethane solution, Chris Bonn 5516S [trade name, manufactured by Dainippon Ink and Chemicals, Inc.] so that the coating thickness would be 20 μm, and in a hot air dryer.
After drying at 130 ° C for 2 minutes, the physical properties of this product were examined. The peeling force was 15g / 3cm and the peeling force after repeated use was 14g / 3cm, and there was no silicone stain on the peeled polyurethane surface. The paintability of the paint was also good.

Example 2 A process release paper was prepared in the same manner as in Example 1 except that Siloxane A in Example 1 was changed to Siloxane B, and its physical properties were examined. As a result, the gloss was 100 gloss and the release force was 13g / 3cm, 11g repeated 3rd peel force
At / 3 cm, this too did not cause silicone stains.

Example 3 A process release paper was prepared in the same manner as in Example 1 except that Siloxane A was changed to Siloxane C, and its physical properties were examined. The gloss was 105 gloss and the release force was 12 g / 3 cm. Then, the peeling force of the third time repeatedly was 10 g / 3 cm, which did not cause silicone stain.

Example 4 A process release paper was prepared in the same manner as in Example 1 except that Siloxane A was changed to Siloxane D, and its physical properties were examined. As a result, the gloss was 101 gloss and the release force was 16g / 3cm, 17g repeated 3rd peel force
At / 3 cm, this too did not cause silicone stains.

Comparative Example Instead of siloxane A in Example 1, the following formula The process release paper was prepared in the same manner as in Example 1 except that the organopolysiloxane (siloxane E) represented by the formula (1) was used, and its physical properties were examined.
Although it was a gloss and the peeling force was 10 g / 3 cm and the peeling force of the third cycle was 18 g / 3 cm, silicone stains were observed on the peeled polyurethane surface and cissing was generated on the paint-coated surface.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display part D21H 27/00

Claims (1)

[Claims] (A) 99 to 70 parts by weight of alkyd resin or acrylic resin, (b) 9.4 mol% or more of organic groups bonded to silicon atoms in one molecule are represented by the formula (Wherein R ¹ is a hydrogen atom, a methyl group or an ethyl group, and n is 0 to 5) is a phenyl group-substituted alkyl group,
At least one of the remaining organic groups is an organopolysiloxane having a hydroxy group-substituted alkyl group represented by the formula CH ₂ —CH ₂ —CH ₂ —OC ₂ H ₄ OmH (where m = 0 to 3). Parts by weight, (c) 15 to 150 parts by weight of alkanol-modified amino resin, and (d) 1 to 20 parts by weight of acidic catalyst, a resin composition for process release paper.