JPH0317146A - Resin composition for industrial release paper - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in gloss, release properties and heat resistance and free from silicone stain by compounding an acrylic resin, an organopolysiloxane, an alkanol-modified aminoresin and an acid catalyst. CONSTITUTION:With (A) 99-70 pts.wt. alkyd resin or acrylic resin, (B) 1-30 pts.wt. organopolisiloxane where >=9.4mol% organic groups bonded to silicon atoms in one molecule are phenyl-substituted alkyl groups represented by formula I (R<1> is hydrogen atom, methyl or ethyl; n is 0-5) and >= one of the rest of the organic groups are hydroxyl-substituted alkyl groups expressed by formula II (m=0-3), (C) 15-150 pts.wt. alkanol-modified amino resin and (D) 1-20 pts.wt. acid catalyst are blended.

Description

DETAILED DESCRIPTION OF THE INVENTION (A field of application) The present invention provides a resin composition for process release paper, particularly for synthetic leather, as it has excellent release properties and gloss at high temperatures and does not cause silicone stains. (Conventional technology) Conventionally, as a resin composition for making the surface of process paper releasable (peelable), 3 fl of polybrobylene type, amino alkyd resin type, and silicone type are known as representative ones.

However, these have advantages and disadvantages; polypropylene-based materials have excellent long-lasting removability when used repeatedly, but there are limits to their use at relatively high temperatures.
In this case, the peeled surface is easily damaged, and enamel (highly glossy) type products (synthetic leather, etc.) cannot be obtained. On the other hand! Although silicone-based products have poor IJII properties and are excellent in terms of releasability, they have drawbacks such as poor gloss and are therefore unsuitable for use in enamel-type synthetic leather. First, 15 to 50 mol% of all organic groups bonded to silicon atoms are phenyl groups, and other organic groups are }10-R- (S) . -R- (where R is a divalent hydrocarbon group, a is O or 1) A silicone-modified alkyd resin or a silicone-modified acrylic resin modified with organoborisiloxane, which is a hydroxy group-substituted organic group, and a polyisocyanate compound. (Special Publication No. 58-53680, Japanese Patent Publication No. 57-480)
See Publication No. 13), and a composition in which an alkanol-modified amino resin and an acidic catalyst are added to this silicone-modified alkyd resin or silicone-modified acrylic resin (Japanese Patent Publication No. 8
3-32825 and Japanese Patent Publication No. 61-13507).

(Problem to be Solved by the Invention) However, although all of these compositions have excellent releasability at high temperatures and give good gloss, these silicone-modified alkyd resins and silicone-modified acrylic resins are organoborisiloxanes. Because the content of the above-mentioned hydroxy-substituted organic group in CH is likely to fluctuate during synthesis, it is difficult to obtain products of consistent quality.In order to overcome this drawback, this hydroxy-substituted organic group is
2CH2CH2 0 Shin CJ4 Kano'it{, (ff
If it is represented by l-0 to 3), a large amount of impurities not containing this group are produced, which has the disadvantage of easily causing silicone stains. (A Thousand Steps to Solve the Problem) The present invention is a process III that solves these disadvantages and drawbacks.
! ! This relates to a paper resin composition, which consists of (a) 99 to 70 parts by weight of an alkyd resin or acrylic resin, (0) an organic group bonded to a silicon atom in one molecule (where R' is a hydrogen atom); , methyl group or ethyl group, n is O~
5) is a phenyl-substituted alkyl group, and at least ! of the remaining organic groups! 1 to 301i parts of an organopolysiloxane which is a hydroxy-substituted alkyl group represented by the formula -C}h-CL-CLOncJ40h}I (herein 1-0 to 3); (iii) alkanol-modified amino resin 15 ~l50! and (di) acidic catalyst 1 to 20 parts by weight.

That is, as a result of various studies in order to develop a resin composition for process release paper that does not involve the disadvantages described above, the present inventors have found that the above-mentioned silicone-modified alkyd resin and silicone-modified acrylic resin have been replaced with alkyd resin or acrylic resin. If it is made of a resin, an organoborisiloxane containing a phenyl-substituted alkyl group, and a hydroxy-substituted alkyl group, and an alkanol-modified amino resin and an acidic catalyst are added thereto, this is a process using a conventionally known resin composition. Compared to release paper, it has better gloss, releasability, and heat resistance, and is a process that does not cause silicone stains! It has been discovered that a resin composition for lI release paper can be obtained,
The present invention was completed by conducting research on the composition of the organoborisiloxane used here. (Function) As described above, the resin composition for process release paper of the present invention has (a) an alkyd resin or an acryl resin, and (b) an organic group bonded to a silicon atom in one molecule of 9.4 to 49.8. Organoborisiloxane in which mol% is a phenyl-substituted alkyl group and other organic groups are hydroxy-substituted alkyl groups, (
c) an alkanol-modified amino resin; and (di) an acidic catalyst.

The alkyd resin and acrylic resin used as the precept in (a) may be of conventionally known types. Therefore, this alkyd resin can be produced by a normal synthesis reaction, that is, by reacting a polyhydric alcohol with a fatty acid, a polybasic acid, etc. Polyhydric alcohols such as glycols and glycerin, trimethylolbroban, trimethylolethane, bentaerythritol, etc. and saturated fatty acids such as octylic acid, lauric acid, valmitic acid, coconut oil, coconut oil fatty acids, castor oil, castor oil fatty acids, large Unsaturated oils like soybean oil, soybean oil fatty acids etc. and fatty acids like unsaturated oil fatty acids etc., polybasic like phthalic anhydride, isophthalic acid, adivic acid, maleic anhydride, fumaric acid, trimellitic anhydride etc. A general method of mixing acids in a predetermined ratio and carrying out a heating condensation reaction may be used, but the fatty acid used here has an oil length of O to 60, preferably 20 to 40, from the viewpoint of peelability, coating performance, etc. is suitable, and the reaction ratio of this polyhydric alcohol, fatty acid, and polybasic acid is OH/C00
}1 equivalent is 1.0 to 1.11, preferably 1.2 to 1.4
It is preferable to do so.

Further, this acrylic resin may be made by a known method, so it may be one obtained by solution polymerization, suspension polymerization, or emulsion polymerization of acrylic monomers. Next, in the organopolysiloxane as component (0) constituting the composition of the present invention, 9.4 to 49.8 mol% of the organic groups bonded to silicon atoms in one molecule are 2Cs}Is-f
cn, soup CH{:}Ia-...(1) Rl, where R+ is a hydrogen atom, a methyl group or an ethyl group,
It is a phenyl-substituted alkyl group with nmo~5, and at least one of the remaining organic groups has the formula ? }lx C82 C}I20 @CzH40
(2) H: It is required to be a hydroxy group-substituted alkyl group in which one is θ to 3, and the remaining organic groups are methyl, ethyl, probyl,
Alkyl groups such as butyl groups and octyl groups, alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups and tolyl groups, or hydrogen atoms bonded to carbon atoms of these groups are replaced with halogen atoms, cyan groups, etc. It may be an unsubstituted or substituted monovalent hydrocarbon selected from a substituted chloromethyl group, trifluorobrobyl group, cyanethyl group, etc., but it is preferably a methyl group.

The molecular structure of this organopolysiloxane is what gives the composition of the present invention heat resistance, good gloss, and excellent releasability. The resin may have a branched structure or a branched structure, but it is desirable that it has excellent compatibility with the alkyd resin and acrylic resin as the component (a). Therefore, preferred organopolysiloxanes are represented by the formula, where R2 is a phenyl-substituted alkyl group represented by the above formula (1), R3 is an organic group, and at least one of these is represented by the above formula (2). The hydroxy group-substituted alkyl group, f+k, is 5 to 1,000 and is 2/2 (Q+k
), if it is 0.15 or less, there will be more repellency, and if it is 0.15 or less, there will be more repellency.
If the value is 5 or more, the synthesis itself becomes difficult, so 0.15 to 0.
．． However, if the content of the phenyl group-substituted alkyl group in this organopolysiloxane is less than 9.4 mol%, repellency will increase, so it is 9.
The reason why at least one of the remaining organic groups is a hydroxy-substituted alkyl group represented by the above formula (2) is because if such an organopolysiloxane is not used, This is because the properties such as releasability, gloss, and repellency when used for synthetic leather will not be satisfactory.

Incidentally, such an organoborisiloxane is an organohydrodiene polysiloxane containing a k hydrogen atom bonded to a silicon atom, and C8H♂CHzh C- as a phenyl group-substituted alkyl group-containing compound represented by formula (1).
CH2 and hydroRl represented by formula (2) CH2.C as a compound containing an alkyl group substituted with an xy group}
I-Clh-0(C2H40). It can be obtained by adding a predetermined amount of H and conducting an addition reaction using a platinum-based catalyst such as chloroplatinic acid. Since the content of the alkyl group and the hydroxy group-substituted alkyl group represented by formula (2) is contained in an amount with little fluctuation, it is possible to easily obtain an organoborisiloxane with stable quality. There is no need to modify the alkyd resin or acrylic resin in advance by cooking, and the composition can be made into a resin composition for process release paper with excellent physical properties by simply cold blending. Furthermore, as the alkanol-modified amino resin as component (c) constituting the composition of the present invention, any commercially available resin can be used, including methoxymethylol melamine resin, plastic Examples include toxymethylol melamine resin, ptoxymethylol urea-melamine cocondensation resin, and butoxymethylol benzoguanamine resin.

The acidic catalyst as component (2) constituting the composition of the present invention may be any of those commonly used for aminoalkyd resins, such as valatoluenesulfonic acid and hydrochloric acid. The resin composition for process release paper of the present invention comprises the above-mentioned (i) alkyd resin or acrylic resin, (0) organopolysiloxane, (c) alkanol-modified amino resin, and (c) alkanol-modified amino resin.
2) It can be obtained by mixing a predetermined amount of an acidic catalyst, and this amount is a mixture of (a) alkyd resin or acrylic resin as a precipitant and (b) an organoborisiloxane as a precipitant. If the amount of organoborisiloxane in parts is less than 1 part by weight, poor peeling will occur, and 30! If the amount exceeds 1 part, the compatibility deteriorates, so (b) 1 to 30 parts by weight of luganoborisiloxane as component to 99 to 70 parts by weight of alkyd resin or acrylic resin as component (i). It is necessary to Also, the mixture 1003 of this component (A) and (kuchi) Bokubu! If the amount of alkanol-modified amino resin added as component (c) is less than 15 parts by weight, the gloss will deteriorate, and if it is more than 150 parts by weight, peeling will be poor, so it should be 15 to 150! If the amount of acidic catalyst as component (2) is less than 1 part by weight per 100 parts by weight of the mixture of (a) kibun and (ku) kibun, curing will be poor; If the amount is more than 20 parts by weight, peeling will be poor, so the amount should be 1 to 20 parts by weight. It should be noted that the mixing ratio of each precept (a), (0), (c), and (2) needs to be within this range because if it is out of these ranges, it will not be possible to obtain the above-mentioned preferable physical properties. However, if necessary, known silicone-modified alkyd resins may be used. Blending silicone-modified acrylic resin is optional. It is convenient to use the resin composition of the present invention in the form of a solvent solution, and the solvent used for this purpose is one that does not have reactivity with (a) the component or (b) the component. This includes benzene, toluene, xylene, methanol, ethanol, isobutanol, n-butanol, methethyl ketone, acetone, tetrahydrofuran, etc. ! Alternatively, a mixture of 2 fl or more is exemplified, but the amount used is usually such that the resin solid content is 10 to 6 fl.
It may be within the range of 0%.

The resin composition obtained by the above method is applied to coated paper, and! By heating and curing at 30 to 200°C, a process paper with a glossy surface with excellent release properties is obtained. It does not generate stains and has excellent removability and heat resistance, and when producing synthetic leather, it can be treated at high temperatures for a short time, so it can be expected to streamline production.

In addition, the resin composition for process release paper of the present invention has a strong coating film and is excellent in repeated removability, so it can be used in a new release agent composition that can be applied to everything from enamel types to matte types containing matting agents. It is a thing.

(Example) Next, examples of synthesizing organopolysiloxane used in the production of the process release paper resin composition of the present invention and examples of the present invention will be given. Measured values are shown in °C.

Synthesis Example 1 Both ends of the molecule are blocked with trimethylsilyl groups,
The molecule contains a hydrogen atom bonded to a silicon atom, and the hydroxyl value of this product was 7.8KOH mg/7g, so it was confirmed that each molecule contained two hydroxyl groups. Example 2: Both ends of the molecule are blocked with trimethylsilyl groups,
Methylhydrodiene polysiloxane 160, which contains a hydrogen atom bonded to a silicon atom in the molecule and is represented by the following formula:
．． A mixture of 195.9 g of α-methylstyrene and 0.01 g of chloroplatinic acid was added dropwise to 9 g at 80°C.
After reacting at 20°C for 8 hours, a mixture of 9.9 g of allyl glycol and 0.0 O1 g of chloroplatinic acid was added dropwise, and the mixture was reacted at 80 to 120°C for 8 hours, and then the reaction product was treated in a conventional manner. , 55.3 mol% of all organic groups bonded to silicon atoms are methyl groups, 32.8 mol%
is a phenyl group-substituted alkyl group, and the viscosity is 10. lO
320 g of transparent organoborisiloxane (hereinafter abbreviated as siloxane A), which is Ocp, was added to 192.2 g of methylhydrodiene polysiloxane shown in
212.4g of methylstyrene and 10.0g of allyl glycol.
2g was added dropwise in the same manner as in Synthesis Example 1 and reacted. As a result, 65.5 mol% of the organic groups bonded to silicon atoms were methyl groups, and 32.7 mol% were phenyl-substituted alkyl groups. and the hydroxyl value is 13.5κOH mg/
g, 380 g of organoborisiloxane (hereinafter abbreviated as siloxane B) having a viscosity of 4,850 cp and having approximately 2 hydroxyl groups in each molecule was obtained. Synthesis Example 3 Both ends of the molecular chain are blocked with trimethylsilyl groups,
Methylhydrodiene polysiloxane 156, which contains a hydrogen atom bonded to a silicon atom in the molecule and is represented by the following formula:
．． When 123.5 g of α-methylstyrene and 11.8 g of allyl glycol were added dropwise to 2 g in the same manner as in Synthesis Example 1 and reacted, 75.6 moles of organic groups bonded to silicon atoms were added. % is a methyl group, 21.9 mol% is a phenyl group-substituted alkyl group, and the hydroxyl value is 20.4.
KO}I mg/g, so there are about 2 hydroxyl groups in one molecule, and the viscosity is 1. 270 g of organopolysiloxane (hereinafter abbreviated as siloxane C) having a weight of 890 cp was obtained.

Synthesis Example 4 The α-methylstyrene in Synthesis Example 1 was replaced with styrene 172
．． When processed in the same manner as Example 1 except that the amount was 7g,
Of the organic groups bonded to silicon atoms, 65.3 mol% are methyl groups, 32.8 mol% are phenyl-substituted alkyl groups, and the hydroxyl value is g. 3 Konmg/g, 305 g of organoborisiloxane (hereinafter abbreviated as siloxane D) having a viscosity of 10.620 cp and having about 2 hydroxyl groups in one molecule was obtained. Example 1 32.5 parts of coconut oil-modified alkyd resin, siloxane A1
, 5 parts of methylated melamine resin, 7.5 parts of butylated urea melamine resin and 10 parts of butylated urea melamine resin were mixed, diluted with 40.5 parts of toluene and 8 parts of isobutanol, and then a 50% balatoluenesulfonic acid-methanol solution 2 parts were added and mixed well to make a resin composition.

Next, this composition was applied to Miracoat paper (trade name, manufactured by Kanzaki Paper Co., Ltd.) with a basis weight of 130 g/n'' so that the coating film became IOM, and was heated at 150° C. for 1 minute in a hot air dryer to cure it. When a process release paper was made using this method, the gloss of this paper was 102 gloss (at 20° C.).

Next, a one-component polyurethane solution, Crysbon 5516S [trade name, manufactured by Dainippon Ink Chemical Co., Ltd.], was applied to this release paper so that the film thickness was 20 μm, and the film was heated at 130°C in a hot air dryer. After drying for 2 minutes, I examined the physical properties of this product and found that the peeling force was 15g/3cm, and the peeling force after the third repeated use was also 14g/73cm.There was no silicone stain on the peeled polycrethane surface, and it was difficult to apply paint. The characteristics were also good. Example 2 A release paper was made using IAI!J in the same manner as in Example 1 except that siloxane B was used instead of siloxane A in Example 1. When the physical properties of this paper were examined, it was found that the gloss was 100.
With gloss, the peeling force was 13g/3cm, and the peeling force for the third repetition was also 11g/73cm, which also did not cause silicone stains.Example 3 Example 1 except that siloxane A was replaced with siloxane C. A process release paper was prepared in the same manner as in step 1, and its physical properties were examined. The gloss of this paper was 105 gloss, and the peeling force was 12 g 73 cm. Although it was repeated, silicone stains were observed on the peeled polyurethane surface, and the paint Repellency occurred on the painted surface.

The third peeling force was also 10g73cm, and this also did not cause any silicone stains. Example 4 A process release paper was prepared in the same manner as in Example 1 except that siloxane D was replaced with siloxane A in Example 1. When the physical properties of this paper were examined, the gloss was 101 gloss and the peeling force was 1. II! g/3 cm, the peeling force for the third repetition was also 17,873 cm, which also did not cause silicone stains.

Comparative example Instead of siloxane A in Example 1, the following formula

Claims (1)

[Claims] 1. (a) Alkyd resin or acrylic resin 99-7
0 parts by weight, (b) 9.4 parts of organic groups bonded to silicon atoms in one molecule
Mol% or more is a formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here R^1 is a hydrogen atom, methyl group or ethyl group,
n is a phenyl group-substituted alkyl group represented by 0 to 5), and at least one of the remaining organic groups is represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where m = 0 to 3) A resin composition for process release paper comprising 1 to 30 parts by weight of an organopolysiloxane which is a hydroxy-substituted alkyl group, (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. .