JPS5853680B2 - Resin composition for process release paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition for process release paper,
More specifically, it is a release agent composition for process paper used when manufacturing synthetic leather by casting method etc. from urethane resin, vinyl chloride resin, polyamide resin, anoic acid resin, etc., and is used as a process release agent. The present invention relates to a new release agent composition that is excellent not only in general quality but also in releasability, particularly releasability at high temperatures, and gloss.

Conventionally, three types of resin compositions, polypropylene-based, aminoalkyd resin-based, and silicone-based, have been known as representative resin compositions for making the surface of processing paper releasable (peelable).

However, although polypropylene-based materials have excellent long-lasting removability when used repeatedly, there is a limit to their use at relatively high temperatures, in which case the removable surface is easily damaged, and the enamel It has the disadvantage that it is not possible to obtain high-gloss) type products (synthetic leather, etc.).

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, and has good release properties. So, this is [in the formula, Me is a methyl group, Ph is a phenyl group, m.

n is a positive integer, m-1-n is 30 to 1000. R' represents an organic group, at least one of which is a divalent hydrocarbon group having a total of 1 to 10 carbon atoms, and a is 0
15 to 50 of the total organic groups bonded to the silicon atom.
Organopolysiloxane in which mole % is phenyl groups 0.
It consists of 100 parts by weight of a silicone-modified alkyd resin modified by 1 to 40% by weight, and (b) 5 to 450 parts by weight of a polyisocyanate compound.

The present invention will be explained in detail below.

The component (a) used in the present invention is a silicone-modified alkyd resin, but the silicone used for this modification is
An organopolysiloxane having a linear structure having a group of formula (II) represented by the general formula (I), in which at least one of the organic groups represented by R1 bonded to a silicon atom is It is a hydroxy group-substituted organic group represented by the above formula (II).

In formula (n) showing this organic group, R is a divalent hydrocarbon group having 1 to 10 carbon atoms in total, a is O or 1, and such an organic group is -CH2CH2-2-CH2C
H2CH2-2-(CH2)b-8-(CH2).

(b is 1 or 2. c is 2 or 3) is exemplified. In this organopolysiloxane, 15 to 50 mol% of the organic groups bonded to silicon atoms are phenyl groups, and R1
Other groups included in this include methyl group, ethyl group,
Examples include alkyl groups such as octyl groups, alkyl groups substituted with halokenes, cyan groups, etc.

As mentioned above, m and n in formula (I) have a sum of 30 to 1.
000, more preferably 50 to 200
is within the range of

The silicone-modified alkyd resin modified with the organopolysiloxane used in the present invention is clearly different from conventional silicone-modified alkyd resins that utilize silanol groups or silicon-bonded alkoxy groups.

The reason for using the organopolysiloxane having a hydroxyl-substituted organic group of the formula (It) in the present invention is that the presence of the hydroxyl-substituted organic group of the formula (II) creates a chemical bond with the alkyd resin. As a result, a silicone-modified alkyd resin can be obtained that can satisfy the properties suitable for use in process release papers, such as release properties, gloss, and repellency against synthetic leather resins, and that the amount of phenyl groups is It is 15 mol% or less,
The compatibility with alkyd resin becomes poor (15 mol%
If the content is more than 50 mol %, the compatibility with the alkyd resin will improve), whereas if it is more than 50 mol %, the intended peeling performance will be poor.

The method for obtaining the silicone-modified alkyd resin, component (a), using the above organopolysiloxane is as follows:
The main methods are (1) the usual synthesis reaction for obtaining alkyd resins, that is, the method of simultaneously reacting the organopolysiloxane as an alcohol component when reacting a polyhydric alcohol with a fatty acid, a polybasic acid, etc.; There are two methods for reacting general alkyd resins with organopolysiloxanes.

The fatty acids used in the 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. fatty acids, castor oil,
Examples include unsaturated oils and unsaturated oil fatty acids such as castor oil fatty acids, soybean oil, soybean oil fatty acids, etc., but from the viewpoint of peelability and coating performance, the oil length is 0 to 60, preferably 2.
A value of 0 to 40 is suitable.

In addition, polybasic acids include phthalic anhydride, isophthalic acid,
Examples include 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.

Method (1) may be a general method of mixing components such as fatty acids, polybasic acids, polyhydric alcohols, and organopolysiloxanes in a predetermined ratio and carrying out a heating condensation reaction. A method may also be used in which a component such as a basic acid is first reacted with the organopolysiloxane, and then a polyhydric alcohol and a polybasic acid are added and the heating condensation reaction is carried out again.

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 50% by weight based on the solid content of the silicone-modified alkyd resin finally obtained.
It is desirable to use it preferably in a range of 0.1 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 an organopolysiloxane.The alkyd resin used at this time has an oil length of 0 to 60, preferably 20 to 40. , coconut oil or coconut oil fatty acids, soybean oil or soybean oil fatty acids, castor oil, castor oil fatty acids, having an acid value of 1 to 30, preferably 5 to 25, and a hydroxyl value of 50 to 300, preferably 100 to 300.
Those manufactured using rice bran oil fatty acids are preferable.

The reaction temperature for reacting organopolysiloxane with such an alkyd resin is usually 60 to 200°C, preferably 100 to 180°C, and the progress of the reaction can be monitored by measuring the viscosity, acid value, and hydroxyl value from time to time. This can be confirmed by

Therefore, the heating condensation reaction may be continued until these values reach the desired values.

The amount of organopolysiloxane used is 0.1 to 50% by weight, preferably 0.1 to 50% by weight based on the solid content of the silicone-modified alkyd resin finally obtained, as in the method (1) above.
．． It is desirable that the content be 1 to 40% by weight.

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

Next, as the polyisocyanate compound which is the component (b), tolylene diisocyanate), 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, etc. may be used as they are or in a mixture. However, from the viewpoint of toxicity and storage stability, for example, desmodule TT, desmodule L1 desmodule N1 desmodule I
It is preferable to use a polyhydric alcohol adduct of diisocyanate such as L, 7' Smodyur HL (manufactured by Bayer AG, trade name), a dimer or a polymer of diisocyanate.

The blending ratio of component (a) and component (b) is 1 of component (a).
It is desirable that the component (b) be in the range of 5 to 450 parts by weight per 00 parts by weight; outside this range, it will not be possible to obtain a process release paper with the desired excellent performance. If necessary, ordinary alkyd resins, acrylic resins, silicone-modified acrylic resins, etc. may be blended into the resin composition for use.

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 component (a) or component (b). For example, one or a mixture of two or more of benzene, toluene, xylene, methyl ethyl ketone, acetone, and tetrahydrofuran can be used.

The amount used should normally be 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,
By heating and curing at 130 to 200°C, a processed paper having a glossy surface with excellent releasability can be obtained.

The process release paper using the resin composition obtained by the present invention has a higher gloss than conventional process paper, and also has excellent peelability and heat resistance. Processing is possible, and rationalization in terms of production can be expected. In addition, the release agent obtained by the present invention has a strong coating film and is excellent in repeated removability, and can be used in all types, from enamel types to matte types containing matting agents. This is a new stripping agent composition that can be applied to

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 dimethylvinylsiloxy groups,
Viscosity 1 whose main chain is composed of 65 mol% dimethylsiloxane units and 35 mol% diphenylsiloxane units
700 g of raw diorganopolysiloxane with 900 centipoise (25°C), 1 2-mercaptoethanol
3. , l, 2 g of benzophenone as a photoreaction accelerator,
Further, 700 g of toluene as a reaction medium was charged into the flask, and then a 100 W high-pressure mercury lamp was inserted into the flask from above and irradiated for 2 hours to cause a reaction.

When toluene was distilled off from the reaction mixture under reduced pressure, it was converted to a hydroxy group-substituted organic compound having the structure shown in the molecule of the raw material diorganopolysiloxane and having a viscosity of 2500 centipoise and having a main chain of the same structure. Group-containing diorganopolysiloxane is 705f! Obtained.

Synthesis Example 2 [Synthesis of organopolysiloxane] Both ends of the molecular chain are blocked with dimethylvinylsiloxy groups,
The main chain is composed of 75 mol% of dimethylsiloxane and 25 mol% of diphenylsiloxane units, and has a viscosity of 10.
1,000 g of raw material diorganopolysiloxane having a centipoise of 0.00 centipoise (25°C), 1 part of 2-mercaptoethanol
6g, benzophenone 4g, and toluene 1000g
was placed in a flask and reacted by irradiation with light in the same manner as in the previous example. The above raw material diorganopolysiloxane was converted to one with the structure shown in 1005.9 of a diorganopolysiloxane containing a hydroxy group-substituted organic group was obtained.

Synthesis Example 3 [Synthesis of organopolysiloxane] Both ends of the molecular chain are blocked with dimethylvinylsiloxy groups,
The main chain is composed of 85 mol% of dimethylsiloxane units and 15 mol% of diphenylsiloxane units, and has a viscosity of 30.
800 g of raw diorganopolysiloxane with 0 centipoise (25°C), 40 g of 2-mercaptoethanol
, 5 g of benzophenone and 800 g of toluene,! i
'f When charged in a flask and irradiated with light to react in the same manner as in the previous example, it was converted to a structure shown by the molecular chain of the raw material diorganopolysiloxane, and the main chain had a similar structure with a viscosity of 800. 830 g of a hydroxy-substituted organic group-containing diorganopolysiloxane having a centipoise (25° C.) was obtained.

Synthesis Example 4 [Synthesis of silicone-modified alkyd resin] 109 parts of hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis Example 1 (indicates parts by weight, the same applies hereinafter),
172 parts of coconut oil fatty acid, 249 parts of phthalic anhydride, and 169 parts of glycerin were charged into a reactor, and after reacting for about 8 hours at an internal temperature of 150-200°C in a nitrogen gas atmosphere, the solid content was reduced to 60% by weight. The mixture was diluted with toluene to obtain 1080 parts of a silicone-modified alkyd resin solution.

The physical properties were as follows.

Synthesis Example 5 [Synthesis of silicone-modified alkyd resin] 32 parts of the hydroxy-substituted organic-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. A silicone-modified alkyd resin solution having a solid content of 60% by weight was obtained by reacting in the same manner as in Synthesis Example 4 and diluting with toluene.
I got 0 copies.

The physical properties were as follows.

Viscosity Acid value Hydroxyl value 2.8 6 Synthesis example 6 [Synthesis of silicone-modified alkyd resin] 30 parts of hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis example 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, and diluted 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 Acid value Hydroxyl value ■~J 3.5 0 Synthesis example 7 [Synthesis of silicone-modified alkyd resin] 29 parts of hydroxy-substituted organic group-containing diorganopolysiloxane obtained in Synthesis example 2, 232 parts of castor oil, phthalic anhydride 215 parts of acid 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 Acid value Hydroxyl value 3 5.8 1 Example 1 73 parts of the silicone-modified alkyd resin liquid obtained in Synthesis Example 4 and 27 parts of Desmodur L were diluted to a solid content of 40%, and coated with this varnish. The coating was coated on paper (manufactured by Kanzaki Seikoki, Miracoat paper, 130 g/rIL2) so that the coating film had a thickness of 10 μm, and was cured in a hot air dryer at 150° C. for 1 minute to obtain a process release paper.

The gloss of this item (Newly manufactured by Murakami Color Technology Research, 75°) is 1
It was 0.2%.

Further, a one-component polyurethane solution (manufactured by Inu Nippon Ink Chemical Industry ■, Crisbon 5516S) was applied onto the release paper so that the film had a thickness of 20μ, and was placed in a hot air dryer at 130°C.
It was dried for 2 minutes and subjected to a peel force test.

The peeling force at this time was 20 g/3 m. The peeling force after repeated use was 55 El/3 Cm.

Example 2 Using 70 parts of the silicone-modified alkyd resin obtained in Synthesis Example 5 and 30 parts of Desmodur L, 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. 102.5%, peeling force 28g/3CrrL,
The peeling force after the third repeated use was 609/3 crn.

Example 3 50 parts of silicone-modified alkyd resin obtained in Synthesis Example 4, 50 parts of Toku7nol 2411-60 [manufactured by Tokushima Essential Oil ■, coconut oil-modified alkyd resin, oil length 33, 60% xylene solution], 40 parts of Desmodur L 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.The gloss was 102%, the peeling force was 32g/3crfL, <
The peeling force at the third use was 6 (1/3 cIrL).

Example 4 35 parts of silicone-modified alkyd resin obtained in Synthesis Example 5, Tesroid 795 [manufactured by Tokushima Essential Oil ■, acrylic resin, viscosity R
A process release paper was prepared in the same manner as in Example 1 using 35 parts of a xylene solution with an acid value of 7.0 and a hydroxyl value of 72.60% and 30 parts of Tesmodur L, and was left for 5 days.

When the gloss and peeling force were measured, the gloss was 101%, the peeling force was 409/3 crrt, and the peeling force after the third repeated use was 90 g/36 rrL.

Example 5 A process release paper was prepared in the same manner as in Example 1 using 35 parts of the silicone-modified alkyd resin obtained in Synthesis Example 7, 35 parts of Tesroid 795, and 30 parts of Desmodur L, and left for 5 days.

When the gloss and peeling force were measured, the gloss was 100%, the peeling force was 251/3 cm, and the peeling force was 50 after repeated use for the third time.
g/3cfrL.

Synthesis Example 8 [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 maintained at 125-130°C. The following mixed components were 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 After finishing adding 2 drops,
The reaction was continued for 5 hours at the same temperature to obtain 755 parts of a silicone-modified acrylic resin liquid.

Solid content 60.5% Viscosity N Hydroxyl value 25 Example 6 Using 43 parts of the silicone-modified alkyd resin obtained in Synthesis Example 6, 29 parts of the silicone-modified acrylic resin obtained in Synthesis Example 8, and 28 parts of Desmodur L, A process release paper was prepared in the same manner as in Example 1, and the gloss and release force were measured.
The gloss was 100%, the peeling force was 2511/3 Cm, and the peeling force at the third repeated use was 50 g/3CrIL.

Comparative Example 1 A process release paper was prepared in the same manner as in Example 1, in which 5 parts of dryer 50 was blended with 100 parts of a glossy aminoacrylic alkyd resin made by Despeel 5P2504C, a release agent for process paper, manufactured by Tokushima Essential Oil ■, and similarly glossy. When the peeling force was measured, the gloss was 98%, the peeling force was 150 g/3 cIfL, and the peeling force at the third repeated use was 300.9/3 cm or more.

Comparative Example 2 35 parts of Toxinol 2411-60, a release agent for process paper,
A process release paper was prepared in the same manner as in Example 1 using 35 parts of Tesroid 795 and 30 parts of Desmodur L, and the gloss and peeling force were measured in the same manner. The peeling force after the third repeated use was 30011/3 or higher.

Claims (1)

[Claims] 1 (a) General formula [wherein Me is a methyl group, ph is a phenyl group, m. n is a positive integer, m-)-n is 30 to 1000. R' represents an organic group, at least one of which is a divalent hydrocarbon group having a total of 1 to 10 carbon atoms, and a is 0
15 of all organic groups bonded to a silicon atom.
A process release paper comprising: 100 parts by weight of a silicone-modified alkyd resin modified with 0.1-40% by weight of an organopolysiloxane in which ~50 mol% is a phenyl group, and (b) 5-450 parts by weight of a polyisocyanate compound. Resin composition for use.