CN1029001C - Adhesion-resisting dealcoholized organosilicon emulsion, preparing process and usage - Google Patents

Adhesion-resisting dealcoholized organosilicon emulsion, preparing process and usage Download PDF

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CN1029001C
CN1029001C CN 90109396 CN90109396A CN1029001C CN 1029001 C CN1029001 C CN 1029001C CN 90109396 CN90109396 CN 90109396 CN 90109396 A CN90109396 A CN 90109396A CN 1029001 C CN1029001 C CN 1029001C
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emulsion
organosilicon
resisting
silicone oil
organotin
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CN1050732A (en
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李平
赵桂荃
刘淑芬
孙红
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Institute of Chemistry CAS
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Abstract

The present invention relates to organosilicon anti-sticking emulsion in a dealcoholization type, and a preparation method and an application thereof. The emulsion is prepared by adding organotin catalyst emulsion and an auxiliary processing agent to polyhydroxy silicone emulsion and alkyl alkoxy silicone emulsion as principal raw materials. Compared with the dehydrogenation antisticking emulsion in common use, the organosilicon anti-sticking emulsion in dealcoholization type has the advantages of equivalent anti-sticking property, easy obtainment of the raw materials, low cost and high stability. Thereby, the organosilicon anti-sticking emulsion in a dealcoholization type can be used for the anti-sticking processing of various kinds of base paper, various plastics and metal films, etc.

Description

Adhesion-resisting dealcoholized organosilicon emulsion, preparing process and usage
The present invention relates to paper release silicone and method for making and purposes that a kind of paper, plastics and metallic film release treatment are used.Specifically, after emulsion of the present invention is coated the surface of above-mentioned base material,, can discharge small molecular alcohol and form the crosslinked silicon rubber film of one deck at substrate surface by thermal treatment, make it to become separate paper and antiseize membrane, can be used for the protection of non-setting adhesive adhesive surface; The packing of pitch, rosin, unvulcanized rubber class viscous substance; The demoulding of imitation leather; And some other needs prevent the agglutinating occasion.
The line style terminal hydroxy group dimethyl-silicon oil molecule of high molecular (several ten thousand to tens0000) after the linking agent reaction, can form partial cross-linked Elastic Film.It has the characteristics of organosilicon macromolecule, i.e. good heat resistance, surface tension low (about 22 dynes per centimeter); incompatible with most of organic polymers; be the ideal non-stick material, behind the surface attached to paper, plastics and metallic film, can be used as the protecting materials of non-setting adhesive glue face.The appearance of paper release silicone just just makes non-setting adhesive winning post paper, non-setting adhesive tape, non-setting adhesive wallpaper and so on non-setting adhesive commodity be greatly developed.
Classify according to product form, paper release silicone can be divided into solvent-borne type, emulsion-type and no-solvent type three classes; Press mechanism of crosslinking classification, can be divided into add-on type and condensed type two classes, wherein the difference of the small molecule by-product that falls by condensation of condensed type product can be divided into two kinds of dehydrogenation and dealcoholizing-types again.The dealcoholizing-type release agent is compared with dehydrogenation type release agent, and raw material is easy to get, low price, but have only the solvent-borne type product to come out so far.And the solvent-borne type release agent catches fire in use easily, contaminate environment, and rate of crosslinking is also not ideal enough simultaneously, causes production rate to descend, and production efficiency is lower.
The object of the present invention is to provide a kind of adhesion-resisting dealcoholized organosilicon emulsion and method for making thereof.This antiseized emulsion had both kept that dealcoholizing-type release agent raw material is easy to get, advantages of cheap price, have emulsion-type release agent production safety, characteristic free from environmental pollution again, its antiseized and processing performance is equivalent to the antiseized emulsion of external dehydrogenation type (with reference to U.S. Pat P4,426,490).
According to method of the present invention, dehydrogenation type anti-adhesive silicone emulsion is mainly by forming as the lower section: high stability polyhydric silicon emulsion, alkyl alkoxy silicone oil emulsion, organotin catalysts emulsion and other auxiliary agents.They are mixed by a certain percentage, just constituted adhesion-resisting dealcoholized organosilicon emulsion.
The used high stability polyhydric silicon emulsion of the present invention is pressed the method preparation of Chinese patent CN85100879B, and wherein the structural formula of silicone oil can be represented by the formula:
Figure 901093963_IMG3
N/m=0.001 in the formula~0.01, better effects if when n/m=0.002~0.005; M-n=1350~2700, performance is better when m+n=1700~2000.
The high stability polyhydric silicon emulsion that the present invention is used, very high placement and shear stability are not only arranged, and owing to activated silica hydroxyl contained in the molecular chain of silicone oil is more than general hydroxy silicon oil, so easier film-forming, can be under lower temperature, or in short heat-up time, form the organosilicon elastica.At this moment guarantee the anti-adhesion effects of separate paper and enhance productivity very important, in addition, generally with D 4(or mixed methylcyclosiloxane) is in the hydroxy-silicone-oil emulsion of raw material with emulsion polymerisation process production, because the equilibrium property of polyreaction exists about ring body of about 15% all the time in hydroxy silicon oil, they are when the release agent film-forming, and Jiang Tongshui is fallen by baking together.This is not only very big waste, and if have that ring body is remaining to get off, be easy to move to the non-setting adhesive face and influence performance.Use low-molecular-weight hydroxy silicon oil to replace D 4Can make as raw material that the content of ring body drops to below 2% in the hydroxy silicon oil, but will prepare low-molecular-weight hydroxy silicon oil specially, China does not still have mass production at present.Employing contains ring body (less than 1%) hardly according to the high stability polyhydric silicon emulsion of the method preparation of Chinese patent CN85100879B, and this has just been avoided waste, has prevented that the transfer because of ring body from reducing the cohesive force of non-setting adhesive.In adhesion-resisting dealcoholized organosilicon emulsion of the present invention, the consumption of high stability polyhydric silicon emulsion generally accounts for the 40~90%, 50~80% better of organosilicon total amount, and preferably 70~80%.
The used alkyl alkoxy silicone oil emulsion of the present invention is to be general expression
Figure 901093963_IMG4
Alkyl alkoxy silicone oil mix with suitable emulsifying agent and water after machinery emulsification and getting.In the formula: R can be methyl, ethyl, phenyl, vinyl, 3.3.3.-trifluoro propyl; R ' is methyl, ethyl, beta-hydroxyethyl, 'beta '-methoxy ethyl; N=3~6.Being used for the emulsifying agent of emulsification alkyl alkoxy silicone oil, all is commercially available negatively charged ion, positively charged ion or nonionic emulsifying agent.For example carbonatoms is sodium salt, sylvite and the ammonium salt of 8~18 alkylsurfuric acid, alkylsulphonic acid, alkyl benzene sulphonate (ABS); The quaternary ammonium salt that general expression is following: [C nH 2n+1N(CH 3) 3] X, [C nH 2n+1(C mH 2m+1) N(CH 3) 2] X, [C nH 2n+1N(CH 3) 2CH 2C 6H 5] X, [C nH 2n+1N ] X, n=12 in the formula~18, m=8~18, n can be identical with m, also can be inequality; Nonionic emulsifying agent can be Fatty Alcohol(C12-C14 and C12-C18) polyoxy ethylene ethers, alkylphenol polyoxyethylene ethers, Tweens and polyvinyl alcohol.Above-mentioned emulsifying agent can use separately, also can be anionic emulsifier and cationic emulsifier respectively with the compound use of nonionic emulsifying agent.The consumption of emulsifying agent or compound emulsifying agent generally is 3~20% of an alkyl alkoxy silicone oil weight, is more preferably 5~10%.The content of alkyl alkoxy silicone oil emulsion can be 10~60%, is generally 20~50%, is preferably 30~40%, and the emulsion of gained is all very stable.
Used equipment can be colloidal mill, ultrasonic emulsator and high pressure homogenizer when preparing the alkyl alkoxy silicone oil emulsion with method of the present invention.As long as emulsifier type of selecting for use and quantity are suitable, correct emulsifying process is arranged again, the alkoxyl silicone fat liquor of gained just has particle little (<1 μ m) so, and highly stable characteristics are placed also not variation in 5 years in room temperature.This generally can only deposit with the containing hydrogen silicone oil emulsion and compare in 3~6 months, and stability improves a lot.In adhesion-resisting dealcoholized organosilicon emulsion of the present invention, it is better that the consumption of alkyl alkoxy silicone oil emulsion generally accounts in the release agent 10~60%, 15~50% o'clock performances of organosilicon total amount, and optimum amount is 20~30%.
The used crosslinking catalyst of the present invention is the organo-tin compound emulsion, and generally the organo-tin compound as the room temperature vulcanized silicone rubber catalyzer all can use.For example dibutyl tin dilaurate, dioctyl two lauric acid tin, dibutyl two butyl maleate tin, dioctyl two butyl maleate tin, dibutyl two single-ethylhexyl maleate tin, dioctyl two single-ethylhexyl maleate tin, dibutyl-S, S '-dimercapto 2-ethyl hexyl ethanoate tin, dioctyl-S, S '-dimercapto 2-ethyl hexyl ethanoate tin, dioctyl two ethyl maleate tin, dioctyl two capric acid tin.With above-mentioned negatively charged ion, positively charged ion or nonionic emulsifying agent or negatively charged ion and nonionic, positively charged ion and nonionic, the mixture of nonionic and nonionic emulsifying agent, can be emulsified into stable emulsion to organo-tin compound, granularity is less than 1 μ m, the content of organotin is generally 10~60% in the emulsion, and preferably 35~50%.In adhesion-resisting dealcoholized organosilicon emulsion of the present invention, it is better that the consumption of organotin generally accounts for 3~20%, 5~15% o'clock performances of organosilicon consumption, and optimum amount is 7.5~10%.
The adhesion-resisting dealcoholized organosilicon emulsion of being formed by high stability polyhydric silicon emulsion, alkyl alkoxy silicone oil emulsion and organotin emulsion provided by the present invention, be applicable to various basic paper and multiple film base paper, and polyester film, polyvinyl chloride film and metallic film.In order to prevent that release agent from infiltrating through basic paper, and the glue spread that helps controlling release agent, can use an amount of tackifier, for example carboxymethyl cellulose, sodium alginate, polyvinyl alcohol join in the antiseized emulsion, to improve its viscosity.Antiseized emulsion ideal viscosity will be different with the difference of antiseized base material, general η 25 ℃The result that can be satisfied with during=3~15 centipoises works as η 25 ℃During=5~8 centipoises, most base materials there is better effect.
According to method of the present invention, after only needing will above-mentioned each component to dilute, mix to obtain antiseized emulsion while stirring by following order: tackifier water solution ← polyhydric silicon emulsion ← alkyl alkoxy silicone oil emulsion ← organotin emulsion ← surplus water with suitable quantity of water.Organosilyl content is generally 5~15% in the antiseized emulsion, and performance was better in 7.5~10% o'clock.After coating the antiseized emulsion that makes like this above the base material, baked 2.5 minutes~15 seconds, can obtain having the separate paper (or film) of fine non-stick property at 90~160 ℃.
Below be the method for making and the enforcement thereof of adhesion-resisting dealcoholized organosilicon emulsion of the present invention.Used polyhydric silicon emulsion is pressed the method preparation of Chinese patent CN85100879B, and non-setting adhesive adopts the PS-02 acrylic acid or the like non-setting adhesive emulsion of being produced by the Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing.Umber in each prescription all is a weight percentage.Except that specializing, what antiseized basic paper adopted is to give the 80 gram copy papers that are coated with polyvinyl alcohol and produce through Beijing of press polish papermaking one factory.Base paper is being coated release agent and after baking, and places under the room temperature to be coated with the non-setting adhesive emulsion in three days again, and the oven dry back is compound with facial tissue, and with the reciprocal roll extrusion of the rubber roll of two kiloponds three times.Peeling force is produced Instron 1122 general purpose material trier with Britain and is measured, and peel angle is 180 °, and draw speed is the 20cm/ branch, and unit is/2.5 centimetres of grams.Cohesive force is the non-setting adhesive emulsion directly to be coated on the facial tissue dry, and is attached to then on the stainless steel plate and with behind the reciprocal roll extrusion secondary of the rubber roll of two kiloponds, with the same method mensuration, unit is kilogram/and 2.5 centimetres.The residue cohesive force is meant that the non-setting adhesive facial tissue of crossing peeling force through said determination is fitted on the stainless steel plate, with measured cohesive force after the reciprocal roll extrusion of the rubber roll of 2 kiloponds 2 times, with kilogram/2.5 centimetres represent.The cohesive force conservation rate is calculated as follows and gets:
The cohesive force conservation rate=(F)/(Fo) * 100%
In the formula, F: residue cohesive force;
F: not with the cohesive force of the contacted non-setting adhesive of release agent itself.Because the cohesive force of non-setting adhesive is subjected to the influence of factors such as temperature variation bigger, for reducing error, each experiment all redeterminates F.
Embodiment one
35% anionic multi-hydroxy silicone oil (contains CH 3SiO 3/20.2 mol %) 2 parts of emulsions, 0.86 part of the emulsion of 35% methyl ethoxy silicone oil (mean polymerisation degree is 4) that forms for emulsifying agent emulsification with Fatty Alcohol(C12-C14 and C12-C18) polyoxy ethylene ether and Sodium dodecylbenzene sulfonate, be that 0.25 part of emulsion, 2 parts of 5% polyvinyl alcohol water solutions, the water of 40% dioctyl, the two single-ethylhexyl maleate tin that form of emulsifying agent emulsification mixes for 4.89 parts and forms the release agent working fluid with Fatty Alcohol(C12-C14 and C12-C18) polyoxy ethylene ether.It is coated in to give is coated with 3g/m 2On the 80 gram copy papers of polyvinyl alcohol, making organosilyl glue spread is 1g/m 2, in 160 ℃ of bakings, baked 15 seconds again, at room temperature placed then three days.Coat acrylic acid or the like non-setting adhesive emulsion again on adherent layer, glue spread is 25g/m 2, in 140 ℃ of baking ovens, dried by the fire 20 seconds then; Promptly fit with facial tissue after the taking-up, recording peeling force is 8.5g/2.5cm, cohesive force conservation rate>100%.
Embodiment two
Used 2.43 parts of 35% polyhydric silicon emulsions among the embodiment one, be 0.5 part of emulsion of emulsifying agent emulsive 30% methyl ethoxy silicone oil (mean polymerisation degree is 4), be that 0.25 part of emulsifying agent emulsive 40% dioctyl two ethyl maleate tin milk liquid, 1.46 parts of 5% polyvinyl alcohol water solutions, water are hybridly prepared into the release agent working fluid for 5.36 parts with the polyvinyl alcohol that contains 12% acetate groups equally with the polyvinyl alcohol that contains 12% acetate groups.Be coated with 3g/m giving again 2This working fluid of coating on the 80 gram copy papers of polyvinyl alcohol, making organosilyl glue spread is 1g/m 2, baking 20 seconds at 160 ℃ immediately then, room temperature was placed after two days, coated emulsion-type acrylic acid or the like non-setting adhesive on adherent layer, and glue spread is 30g/m 2, 140 ℃ were dried by the fire after 20 seconds, compound facial tissue, and recording peeling force is 10 gram 2.5cm, cohesive force conservation rate>100%.
Embodiment three
Used 2.14 parts of 35% polyhydric silicon emulsions among the embodiment one, 0.71 part of the 35% methyl ethoxy silicone oil emulsion that forms for emulsifying agent emulsification with Fatty Alcohol(C12-C14 and C12-C18) polyoxy ethylene ether and Sodium dodecylbenzene sulfonate, 0.15 part of 50% dibutyl tin dilaurate emulsion, 2 parts of 5% polyvinyl alcohol water solutions, the water that forms for emulsifying agent emulsification with the Sodium dodecylbenzene sulfonate are hybridly prepared into antiseized working fluid for 5 parts.Be coated with 3g/m giving again 2This release agent of coating on the 80 gram copy papers of polyvinyl alcohol, making glue spread is 1g/m 2, in 160 ℃ of baking ovens, baking 15 seconds then, room temperature was placed after three days, coating acrylic acid or the like non-setting adhesive emulsion on adherent layer, glue spread is 25g/m 2, again 140 ℃ of bakings 20 seconds, dry back applying facial tissue, recording peeling force is 15g/2.5cm, the cohesive force conservation rate is 99%.
Embodiment four
Used 1.43 parts of 35% polyhydric silicon emulsions, Fatty Alcohol(C12-C14 and C12-C18) polyoxy ethylene ether and 1.43 parts of sodium lauryl sulphate emulsive 35% methyl ethoxy silicone oil emulsions among the embodiment one, be that 1 part of 10% dioctyl, two capric acid tin milk liquid, 2 parts of 5% polyvinyl alcohol water solutions, the water of emulsifying agent is formed antiseized emulsions for 4.14 parts with the Sodium dodecylbenzene sulfonate.Then it is coated in and gives on the copy paper that scribbles polyvinyl alcohol, 160 ℃ baked 15 seconds, at room temperature placed then three days, were coated with acrylic acid or the like non-setting adhesive emulsion again on adherent layer, and recording peeling force after the oven dry is 10g/2.5cm, cohesive force conservation rate>100%.
Embodiment five
2.14 parts of 35% hydroxy-silicone-oil emulsions, with Fatty Alcohol(C12-C14 and C12-C18) polyoxy ethylene ether, sodium lauryl sulphate and 0.71 part of polyvinyl alcohol (containing the 12mol% acetate groups) emulsive 35% methyl ethoxy silicone oil emulsion, 40% usefulness Fatty Alcohol(C12-C14 and C12-C18) polyoxy ethylene ether emulsive dioctyl-S, S '-0.25 part of dimercapto 2-ethyl hexyl ethanoate tin milk liquid, 1.4 parts of 5% polyvinyl alcohol water solutions, water cooperate for 5.5 parts forms the release agent working fluid.Then it is coated and give the copy paper that is coated with polyvinyl alcohol, baked 15 seconds through 160 ℃, room temperature was placed after three days, coated acrylic acid or the like non-setting adhesive emulsion again on adherent layer, the compound facial tissue in oven dry back, and recording peeling force is 13.7g/2.5cm, the cohesive force conservation rate is 88%.
Embodiment six
0.71 part of 2.14 parts of 35% polyhydric silicon emulsions, 35% methyl ethoxy silicone oil emulsion, 0.25 part of 40% dioctyl, two single-ethylhexyl maleate tin milk liquid, 5% polyvinyl alcohol water solution 2 parts of (except the aluminium platinum example), water used among the embodiment one are hybridly prepared into antiseized working fluid for 4.9 parts.Then it is coated above the various base materials shown in the following table, after roasting, room temperature was placed three days, was coated with acrylic acid or the like non-setting adhesive emulsion again on adherent layer, and in 140 ℃ of oven dry in 20 seconds, compound facial tissue, it is as shown in the table to record performance.
Base material kind precoat bakes condition peeling force cohesive force
G/2.5cm conservation rate %
160 ℃ 15 " 11>100 of 80 gram art paper PVA
160 ℃ 15 " 14>100 of 40 gram writing paper PVA
160 ℃ 15 " 14>100 of 80 gram kraft paper PVA
160 ℃ 15 " 13 85 of 67 gram white board PVA
Multiple PE kraft paper/120 ℃ 2.5 ' 18 98
Polyvinyl chloride film/90 ℃ 2.5 ' 23 97
Polyester film/150 ℃ 20 " 14 97
Aluminium foil/150 ℃ 20 " 17 98

Claims (11)

1, a kind of adhesion-resisting dealcoholized organosilicon emulsion that is applicable to release treatment is characterized in that, it is 10~200,000 polyhydric silicon emulsion by molecular weight and adds emulsifying agent and with mechanical means with general expression be
Figure 901093963_IMG1
The alkyl alkoxy silicone oil emulsification of (n=3~6) and the alkyl alkoxy silicone oil emulsion, organotin catalysts emulsion and the processing aid that make are formed, wherein the consumption of polyhydric silicon emulsion accounts for 40~90% of organosilicon total amount in the release agent, the consumption of alkyl alkoxy silicone oil emulsion accounts for 10~60% of organosilicon total amount, and the consumption of catalyzer organotin hydroxy acid salt emulsion accounts for the 3-20% of organosilicon total amount.
2, according to the described adhesion-resisting dealcoholized organosilicon emulsion of claim 1, the consumption that it is characterized in that employed polyhydric silicon emulsion be in the release agent organosilicon total amount 50~80%.
3, according to claim 1 or 2 described adhesion-resisting dealcoholized organosilicon emulsions, the consumption that it is characterized in that employed polyhydric silicon emulsion be in the release agent organosilicon total amount 70~80%.
4, according to the described adhesion-resisting dealcoholized organosilicon emulsion of claim 3, the granularity that it is characterized in that employed alkyl alkoxy silicone oil emulsion is less than 1 μ m, and wherein the content of alkyl alkoxy silicone oil is 10~60%.
5, according to the described adhesion-resisting dealcoholized organosilicon emulsion of claim 1, employed emulsifying agent can be negatively charged ion, positively charged ion and nonionic emulsifying agent when it is characterized in that emulsification alkyl alkoxy silicone oil, or negatively charged ion and positively charged ion are respectively with the composite blending emulsifiers that forms of nonionic, wherein, anionic emulsifier is that carbonatoms is sodium salt, sylvite and the ammonium salt of alkylsurfuric acid, alkylsulphonic acid and the alkyl benzene sulphonate (ABS) of 8-18, and cationic emulsifier is the following quaternary ammonium salt of general expression: [C nH 2n+1N(CH 3) 3] X, [C nH 2n+1(C mH 2m+1) N(CH 3) 2] X, [C nH 2n+1N(CH 3) 2CH 2C 6H 5] X, [C nH 2n+1N
Figure 901093963_IMG2
] X, n=12 in the formula~18, m=8~18, n can be identical with m, also can be inequality, nonionic emulsifying agent is Fatty Alcohol(C12-C14 and C12-C18) polyoxy ethylene ether, alkylphenol polyoxyethylene ether, Tweens and polyvinyl alcohol, and the consumption of emulsifying agent or compound emulsifying agent is the 3-20% of alkyl alkoxy silicone oil weight, and the consumption of alkyl alkoxy silicone oil emulsion is the 15-50% of organosilicon total amount in the release agent in antiseized emulsion.
6, according to claim 1 or 5 described adhesion-resisting dealcoholized organosilicon emulsions, the consumption that it is characterized in that employed alkyl alkoxy silicone oil emulsion is the 20-30% of organosilicon total amount in the release agent.
7, according to the described adhesion-resisting dealcoholized organosilicon emulsion of claim 1, it is characterized in that used organotin emulsion can be with various organotin-carboxylates with various emulsifying agent with mechanical means emulsification easily, organotin-carboxylate can be a dibutyl tin dilaurate, dibutyl two butyl maleate tin, dibutyl two single-ethylhexyl maleate tin, dibutyl-S, S '-dimercapto 2-ethyl hexyl ethanoate tin, dioctyl two lauric acid tin, dioctyl two capric acid tin, dioctyl two single-ethylhexyl maleate tin, dioctyl two ethyl maleate tin and dioctyl-S, S '-dimercapto 2-ethyl hexyl ethanoate tin, the used emulsifying agent of these organotin-carboxylates of emulsification is a negatively charged ion, positively charged ion and nonionic emulsifying agent or negatively charged ion and positively charged ion are respectively with the composite blending emulsifiers that forms of nonionic, the active constituent content of organotin-carboxylate emulsion is 10-60%, and the consumption of organotin-carboxylate is 5~15% of an organosilicon total amount in antiseized emulsion.
8, according to the described adhesion-resisting dealcoholized organosilicon emulsion of claim 7, the consumption that it is characterized in that employed organotin-carboxylate is 7.5~10% of an organosilicon total amount.
9,, it is characterized in that and to use that also can not use tackifier, the tackifier that use are carboxymethyl cellulose, sodium alginate or polyvinyl alcohol according to the described adhesion-resisting dealcoholized organosilicon emulsion of claim 1.
10, a kind of method for preparing the described adhesion-resisting dealcoholized organosilicon emulsion of claim 1, only needing it is characterized in that with behind the each component dilute with water, mix while stirring by following order and to get final product: tackifier water solution ← polyhydric silicon emulsion ← alkyl alkoxy silicone oil emulsion ← organotin emulsion ← surplus water, organosilyl content is generally 5~15% in the antiseized emulsion.
11, the purposes of the described adhesion-resisting dealcoholized organosilicon emulsion of claim 1 is characterized in that this antiseized emulsion can be used for the release treatment of paper, plastics and metallic film.
CN 90109396 1990-11-27 1990-11-27 Adhesion-resisting dealcoholized organosilicon emulsion, preparing process and usage Expired - Fee Related CN1029001C (en)

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