JPH03255183A - Peeling agent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which needs no heat treatment at high temperature and is improved in peeling function and labor hygiene when used, by using as its constituent an aqueous dispersion obtained by adding a basic compound and water to a specified stirred polymer solution. CONSTITUTION:In the presence of 1-20wt.% polysiloxane containing terminal OH groups and having an average molecular weight of 500 to 1,500,000, 0.05-10wt.% polymerizable silane compound comprising a compound having both polymerizable unsaturated groups and groups capable of undergoing condensation reaction with the polysiloxane, 1-30wt.% unsaturated organic acid, and 40-97.95wt.% other monomer copolymerizable therewith are polymerized in an organic solvent other than alcohol at from room temperature to 200 deg.C give a polymer solution (a). 100 pts.wt. component (a) is mixed with a basic compound (b) in an amount of 20-200mol% based on the acid group of the polymer in component (a) and 30-1,000 pts.wt. water (c) with agitation to give an aqueous dispersion of the basic compound salt of a polysiloxane graft polymer. 100 pts.wt. (on a solid basis) said dispersion is mixed, if required, with 0.01-20 pts.wt. water-soluble resin.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to the basicity of a polysiloxane graft polymer obtained by polymerizing a monomer mixture containing a polymerizable silane compound in the presence of a polysiloxane containing a terminal hydroxyl group. It relates to an aqueous dispersion of a compound, or a release agent composition comprising the aqueous dispersion and a water-soluble resin, which can be applied to the surface of base materials such as various synthetic resin films, cellophane, paper, cloth, etc. The present invention provides a composition that imparts a release function to the surface of a substrate.

[Conventional technology]

Conventionally, three types of release agents have been proposed or put to practical use: long-chain alkyl group-containing polymers, silicone-based polymers, and fluorine-based polymers; There were problems such as migration and high cost. Especially silicone polymers! Although the ls effect is extremely good, there are problems such as the need for heat treatment at high temperatures, the transfer of uncrosslinked silicone to the adhesive layer, resulting in a decrease in adhesion, and poor printability when laminated in two layers.

[Problem that the invention seeks to solve]

As a result of intensive research regarding the above-mentioned stripping agent composition, the present inventors disclosed in JP-A No. 61-215629 that a monomer mixture containing a polymerizable silane compound was polymerized in the presence of a polysiloxane containing a terminal hydroxyl group. We have discovered and proposed that a surface-modified composition containing a polysiloxane graft polymer obtained by the above method has a function as a release agent.

However, although the coating film obtained from this surface-modified composition has sufficiently satisfactory properties depending on the conditions of use, in some cases a higher degree of migration resistance is required. In addition, the polysiloxane graft polymer is essentially a surface-modifying composition containing an organic solvent solution, which poses laborious and hygienic problems in use, and may last for a long time depending on the composition of the polymer. The inconvenience of gelation may occur during storage.

In addition, as an aqueous dispersion of a polysiloxane graft polymer that has been proposed so far, a vinyl polymer having a carboxyl group and a hydroxyl group is produced in a water-dilutable organic solvent, and then a hydroxyl group or an alkoxyl group is added to this. An aqueous dispersion obtained by reacting an organopolysiloxane having
No. 5388) and moisture materials obtained by emulsion polymerization of organopolysiloxanes having polymerizable unsaturated groups and other vinyl monomers in an aqueous medium in the presence of an emulsifier (JP-A No. 51-1
No. 46525), etc. are known. However, in these methods, due to the low reactivity of organopolysiloxane, modification is often incomplete, and in some cases, phenomena such as separation and aggregation easily occur during the reaction. The reality is that in order to stably obtain an aqueous siloxane graft polymer dispersion, there are compositional constraints.

[Means for solving problems]

In view of the current situation, the present inventors conducted extensive research on a release agent composition that does not require high-temperature heat treatment, has an excellent release function, and is free from hygienic problems when used.
We have arrived at the present invention.

That is, in the present invention, in the presence of 1 to 20% by weight of a polysiloxane containing terminal hydroxyl groups (A), 0.05 to 10% by weight of a polymerizable silane compound (B), and an unsaturated organic acid (C).
1 to 30% by weight and other polymerizable monomers (D) copolymerizable with these 40 to 97.95% by weight (However, (A)
, (B), (C) and (D) components is 100% by weight. ) is polymerized in an organic solvent other than alcohol, and a basic compound and wood are added to the polymer solution, which is then stirred. The present invention relates to a stripping agent composition comprising the present invention. A water-soluble resin may be added to the aqueous dispersion, and the amount used is 0 per 100 parts by weight of the aqueous dispersion (solid delivery 3I).
~50 parts by weight.

The terminal hydroxyl group-containing polysiloxane (A) used in the present invention can be used without any restriction as long as it is a linear or partially branched polysiloxane in which at least one terminal is a hydroxyl group. These are easily available and can be used depending on the purpose.

Such terminal hydroxyl group-containing polysiloxane (A)
For example, - formula (where R1 and R2 are each independently a monovalent hydrocarbon group that may be substituted with halogen, R3 is hydrogen or a monovalent hydrocarbon group that may be substituted with halogen, n is an integer of 1 or more).

Branched polysiloxanes having branched parts can also be suitably used.

More specifically, examples include dialkylpolysiloxanes such as diphenylpolysiloxane and methylethylpolysiloxane, alkylarylpolysiloxanes such as methylphenylpolysiloxane, and diarylpolysiloxanes such as diphenylpolysiloxane. One type or a mixture of two or more types selected from these groups can be used.

Among these, linear or partially branched dimethylpolysiloxanes having at least one hydroxyl group at the end are preferred because they can be obtained at low cost and provide polysiloxane graft polymers with excellent performance.

The average molecular weight of the polysiloxane (A) used is in the range of 5,000,000 to 1,500,000, preferably 5,000 to 150,000.
If the average molecular weight is less than 500, the resulting release agent composition may not exhibit the desired release function sufficiently; If it exceeds 1.5 million, the viscosity becomes high and handling and polymerization operations may become difficult.

The amount of the terminal hydroxyl group-containing polysiloxane (A) to be used can be determined as appropriate within the range of 1 to 20% by weight, depending on the degree of peeling effect. If the amount used is less than 1% by weight, the peeling effect will not be sufficient, and if it exceeds 20% by weight, the adhesion to the substrate will decrease, which is not desirable.

The polymerizable silane compound (B) used in the present invention is a compound having in its molecule at least one polymerizable unsaturated group and at least one group capable of condensation reaction with the polysiloxane. Methoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane , γ-(meth)acryloxypropylmethyldimethoxysilane, γ(meth)acryloxypropylmethylethoxysilane, γ-(meth)acryloxypropyltris(β-methoxyethoxy)silane, 2
-Styrylethyltrimethoxysilane, (meth)acryloxyethyldimethyl(3-trimethoxysilylpropyl)ammonium chloride, vinyltriacetoxysilane, vinyltrichlorosilane, etc., and one or two selected from these groups. Mixtures of more than one species can be used.

The amount of the polymerizable silane compound (B) to be used can be determined as appropriate within the range of 0.05 to 10% by weight.

If the amount used is less than 0.055% by weight, polysiloxane (A
) and the polymer consisting of the polymerizable silane compound (B), unsaturated organic acid (C), and polymerizable monomer (D) components are insufficient, and an effective amount of graft reaction does not occur, resulting in an aqueous dispersion. After this, unreacted polysiloxane tends to cause layer separation. Moreover, if the amount exceeds 10% by weight, stability becomes poor and gelation tends to occur during polymerization.

The unsaturated organic acid (C) used in the present invention has the effect of inducing a bond between the polysiloxane (A) and the polymer to smoothly advance the graft reaction, and also dispersing the resulting polysiloxane graft polymer in water. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid, vinyl sulfonic acid, sulfoethyl methacrylate, and 2-acrylamide.
Examples include unsaturated sulfonic acids such as 2-methylpropanesulfonic acid, and IN or a mixture of two or more of these can be used.

The amount of the unsaturated organic acid (C) to be used can be determined as appropriate within the range of 1 to 30% by weight, preferably 3 to 20% by weight. It is difficult to obtain a stable aqueous dispersion when using 1% by weight of the final vortex, and when the amount exceeds 30% by weight, f4
The wood affinity of the resulting polymer becomes too strong, which not only makes stable water dispersion difficult, but also makes it difficult to obtain a release agent composition.
− The water resistance becomes inferior.

Examples of the polymerizable monomer (D) used in the present invention include acrylic esters such as butyl acrylate and 2-ethylhexyl acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; -(Meth)acrylic acid hydroxyalkyl esters such as hydroxypropyl; Methacrylic acid esters such as methyl methacrylate and butyl methacrylate; Vinyl acetate, vinyl propionate and other vinyl esters: Aromatic vinyls such as styrene and vinyltoluene. Types: Unsaturated nitriles such as acrylonitrile and methacrylaterile Unsaturated amides such as niacrylamide and N-methylol acrylamide: α-olefins such as ethylene, propylene, and imbutylene: Methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, etc. Vinyl ethers: #: vinyl tetrachloride, vinylidene chloride, vinyl dihydride, vinylidene dichloride, etc. α,β-unsaturated #i-mers: trifluoroethyl (meth)acrylate, 2゜2.3.3-tetrafluoropropyl acrylate, LH, IH, 2H
, 2H-hebutadecafluoroacyl acrylate, IH
, IH, 5H-octafluoropentyl acrylate and other fluorine-containing (meth)acrylic esters, 2,3,5
．． 6-titrafluorophenyl acrylic acid ester, 2
．． Examples include aromatic fluorine-containing (meth)acrylic esters such as 3,4,5.6-pentafluorophenyl methacrylic ester, and one type or a mixture of two or more of these can be used.

The amount of the polymerizable monomer (D) to be used can be determined as appropriate within the range of 40 to 97.95% by weight. If the amount used is less than 40% by weight or more than 95% by weight, the above-mentioned polysiloxane (A), polymerizable silane compound (B)
Alternatively, the amount of unsaturated organic acid (C) used may be too much or too little from the above-mentioned range, which is undesirable because the above-mentioned drawbacks will occur.

As the organic solvent that can be used during polymerization, any organic solvent other than alcohol, that is, an organic solvent that does not have alcoholic hydroxyl reversion, can be used without any restriction.
Examples include toluene, xylene, benzene, hexane, cyclohexane, trichloroethane, methyl ethyl ketone, ethyl acetate, dioxane, cellosolve acetate, etc. One type or a mixture of two or more of these can be used, but polymer Toluene and xylene are particularly preferred from the viewpoint of solubility, boiling point, etc.

Alcohol-based organic solvents with alcoholic hydroxyl groups, such as methyl alcohol, ethyl alcohol,
Alcohols such as inpropyl alcohol, cellosolves such as methylseronlube and ethylseronlube, etc. are polysiloxane (A), a polymerizable silane compound (B), an unsaturated organic acid (C), and a polymerizable monomer (El Although it cannot be used from the initial stage of polymerization because it inhibits the graft reaction with the polymer consisting of component (), it can be added and used after the graft reaction has sufficiently progressed.

Examples of the polymerization initiator include common radical polymerization initiators such as azobisin butyronitrile and pensoyl peroxide.

The polymerization temperature is usually room temperature to 200°C, preferably 40 to 1
The zero polymerization concentration in the range of 20°C is usually 30-70% by weight.
, preferably 40 to 60% by weight.

As the basic compound for preparing the salt of the polysiloxane graft polymer, any basic compound that has been conventionally used for the purpose of neutralizing acidic substances can be used without any restriction.
Sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine,
Examples include methyldiethylamine, dimethylethylamine, monomethyloldimethylamine, monomethyloldiethylamine, dimethylolmethylamine, and dimethylolethylamine, and one or more of these may be used. The basic compound is used to make the polysiloxane graft polymer water-dispersible, and is preferably used in an amount corresponding to 20 to 200 mol% of the acid groups in the polymer. If the amount is less than 20 mol%, a sufficient aqueous dispersion may not be obtained. In particular, in order to obtain a release agent composition that maintains a good dispersion state even during storage and does not have the disadvantages caused by basic compounds, such as a decrease in aqueous properties and discoloration, It is preferable to add it in an amount corresponding to 50 to 100 mol % of the acid groups. At this time, if a high degree of dispersion stability is required, a suitable emulsifier and/or protective colloid may be used in combination.

The amount of water added is 30 to 1000 parts by weight per 100 parts by weight of the polysiloxane graft polymer solution. 3
If the amount is less than 0 parts by weight, water will not form a continuous phase and a stable aqueous dispersion cannot be obtained. On the other hand, if the amount exceeds 1000 parts by weight, the polysiloxane graft polymer content will be diluted, which is economically undesirable.

In order to stir a liquid containing a polysiloxane graft polymer to form a stable aqueous dispersion, the amount of water-soluble organic solvent in the liquid should be 30-100% by weight based on the total amount of organic solvent.
It is preferable that

When a water-soluble organic solvent is used in an amount of 30% by weight,
Sedimentation of the dispersed particles may occur, and a sufficient aqueous dispersion may not be obtained. The ratio of the water-soluble organic solvent to 30 to 100% by weight of the total organic solvent may be adjusted before or after the addition of water, but preferably before the addition.

Water-soluble organic solvents include lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, cyclic ethers such as tetrahydrofuran and dioxane, ketones such as acetone, and water-dilutable solvents such as selon rubs such as methyl selon rub and ethyl cellosolve. It is an organic solvent.

Considering the residual organic solvent preferably used in polymerization, the proportion of the water-soluble organic solvent is preferably 40 to 90% by weight based on the total organic solvent.

The aqueous dispersion of the salt of the basic compound of the polysiloxane graft polymer thus obtained can be suitably used as it is as a stripping agent composition, but in consideration of environmental protection during use, it is preferable to further remove the solvent. The removal of the solvent can be easily carried out by conventionally known methods such as vacuum distillation, heating distillation, etc. The amount of solvent removed should be appropriately determined depending on the needs, but #1 of the present invention
In order to maximize the effect, it is preferable to remove an amount equivalent to 90% by weight or more contained in the dispersion.

In the present invention, the water-soluble resin is used to further enhance the film-forming properties, hiding properties, adhesion properties, etc. of the aqueous dispersion of the salt made from the basic compound of the polysiloxane graft polymer, and any water-soluble resin can be used without any restriction. For example, polyvinyl alcohol.

Water-soluble acrylic resin, water-soluble polyester resin.

Water-soluble polyamide, water-soluble polyurethane resin.

Examples include polyethylene glycol, polyacrylamide, celluloses, and gelatin.

One kind or a mixture of two or more kinds selected from these groups can be used, and among them, polyvinyl alcohol is preferred because a release agent composition with particularly excellent wettability can be obtained.

When a water-soluble resin is used, the amount used is 50 parts by weight or less, preferably 0.01 to 20 parts by weight, based on 100 parts by weight of the solid content of the aqueous dispersion of the salt of the IM basic compound of the polysiloxane graft polymer. , more preferably 0.1
-5 parts by weight, and if the amount exceeds 50 parts by weight, the water resistance of the release agent composition decreases, which is not preferable.

An aqueous resin composition consisting of an aqueous dispersion of a salt made of a basic compound of a polysiloxane graft polymer and a water-soluble resin is prepared by: 1. An aqueous dispersion of a salt made of a basic compound of a polysiloxane graft polymer and a water-soluble resin are heated at room temperature. 2. A method in which a basic compound, water and a water-soluble resin are added to a solution of a polysiloxane graft polymer and a liquid product is stirred and mixed at room temperature and under heating. It can be preferably manufactured.

The crosslinking agent used in combination with the aqueous resin composition is preferably one that reacts at as low a temperature as possible, such as dimethylol urea and other polymethylol ureas, dimethylol ethylene urea, dimethylol glyoxal monourein, and dimethylol glyoxal. Diurein, dimethyloluron, dimethylolpropylene urea, 1.3-
Bis(hydroxymethyl)-tetrahydro-5-hydroxy-2-pyrimidinone, dimethyloltriazine, dimethylolmelamine and other polymethylolmelamines,
Polymethylol compounds such as polymethylol acetoguanamine polymethylol benzoguanamine; polyaldehyde compounds such as glyoxal, glutaraldehyde, dialdehyde starch Th; 1,8-hexamethylene diethylene urea,! , 1゜1) Polyaziridine compounds such as (ω-aziridinylpropionate) methylpropane: Nonionic water-soluble epoxies such as diglycidyl ether of polyethylene glycol, glycerin diglycidyl ether, trimethylolpropane diglycidyl ether, etc. Water-soluble copolymer of compound glycidyl ester of acrylic acid or methacrylic acid and acrylamide; polyamide epoxy resin; boric acid, borate; Na2ZrSi0
4. Zr0Ca・3H20, ZrOSO4・nH2O
,Zr0(NO3)74H20,Zr0(003)2・
nH2O, ZrO(OH)2 ・nH2O, Zr0(C
2H202)2. (N)14)2ZrO(GO3)2,
A zirconium compound represented by a chemical formula such as ZrSiO4 can be used. In addition, if necessary, a suitable curing accelerating catalyst may be used.The amount of crosslinking agent used is 1 to 30 parts by weight per 100 parts by weight (solid content) of the aqueous resin composition.
The range is preferably parts by weight.

The aqueous dispersion of a salt made from a basic compound of a polysiloxane graft polymer obtained as described above has excellent long-term storage stability, and there is no need for heat treatment at high temperatures. It can form a film with excellent properties, iFI migration properties, etc., and can be suitably used as a release agent composition as it is. However, if necessary, known pigments, toners, lubricants, and plasticizers may be added , a rust preventive agent, an antistatic agent, an antifoaming agent, a viscosity modifier, a wetting agent, a PH modifier, etc. can be blended. It can also be diluted as appropriate.

〔Effect of the invention〕

The release agent composition of the present invention has excellent long-term storage stability, and the coating film obtained by applying it to a substrate does not require heat treatment at high temperatures and has good adhesion to the substrate. Moreover, it exhibits excellent release functions such as good release properties and migration resistance, and exhibits excellent properties when applied to a release agent.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited in any way by these examples, and all parts in each example indicate parts by weight.

Reference example 1 Thermometer, reflux condenser, dropping funnel, nitrogen introduction pipe and pump
10 parts of a 30% by weight toluene solution of a linear dihydroxydimethylpolysiloxane having an average molecular weight of 120,000 as a polysiloxane containing terminal hydroxyl groups and 100 parts of toluene were charged into a four-bottomed flask equipped with a nitrogen atmosphere, and the temperature was raised to 80°C under a nitrogen atmosphere. It was warm. To this, 70 parts of methyl methacrylate, 20 parts of butyl acrylate, 5 parts of acrylic acid,
20% by weight of a homogeneous monomer solution consisting of 5 parts of γ-methacryloxypropyltrimethoxysilane and 2 parts of azobisisobutyronitrile was added and initial polymerization was carried out at 80°C for 30 minutes. The remaining monomer homogeneous solution was added dropwise over 2 hours, and when the polymerization was continued for 2 hours and 30 minutes after the completion of one drop, 10 parts of inpropyl alcohol was added to dilute the solution. Continue to maintain the temperature at 80℃ for 1 hour 30 minutes.
After stirring for several minutes to continue the polymerization reaction, the mixture was cooled and a solution of a polysiloxane graft polymer (hereinafter referred to as 1 polymer solution (1)) was obtained. Obtained polymer solution (1) 4
After diluting by adding 60 parts of inpropyl alcohol to 0 parts,
Three parts of 28% aqueous ammonia were added with stirring, and stirring was continued for 10 minutes, followed by the addition of 237 parts of water to form a water dispersion.

Subsequently, the internal temperature was raised to 60°C, and the temperature was reduced to 25°C by vacuum distillation.
After removing the solvent by distilling off 0 parts, aqueous ammonia and water were added to adjust the pH to 9.0 and the concentration to 30%, and a polysiloxane graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (1)) was prepared.
) was obtained. The obtained aqueous dispersion (1) has a viscosity of 1
At 0 cps (25°C, B-type viscometer, 60 rpm), -
Even after being allowed to stand for a week, the emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane. In addition, the remaining inpropyl alcohol and toluene were 90 ppm and 750 ppm, respectively. To check the storage stability of the solution, it was stored at 50°C for 6 months, and the polymer solution (1) had gelated. However, the aqueous dispersion (1) was stable with no change in viscosity.

Reference Example 2 eInsert Reference Example 1 into a four-lobe flask similar to that used in Example i.
33.3 parts of a 30% by weight toluene solution of the same terminal hydroxyl group-containing polysiloxane as used in 1 and 100 parts of toluene were charged, and the temperature was raised to 80° C. under a nitrogen atmosphere.

To this, 50 parts of methyl methacrylate, 2 parts of butyl acrylate
0 parts, 20 parts of acrylonitrile, 5 parts of acrylic #, γ-
Using a homogeneous monomer solution consisting of 5 parts of methacryloxypropyltrimethoxysilane and 2 parts of azobisinbutyronitrile, the same initial polymerization operation and dropping operation of the homogeneous monomer solution as in Reference Example 1 were performed. When polymerization was continued for 30 minutes after the monomer homogeneous solution was added dropwise, ethyl alcohol 1
00 parts were added and activated. After further continuing the polymerization reaction at 80° C. for 3 hours and 30 minutes, it was cooled and a solution of polysiloxane graft polymer (hereinafter referred to as polymer solution (2)) was prepared.
I got it. The same operation as in Reference Example 1 was carried out except that 2.5 parts of 28% ammonia water was added to 200 parts of the obtained polymer solution (2), and the polysiloxane graft polymer aqueous dispersion (
Hereinafter, aqueous dispersion (2)) was obtained.

The resulting aqueous dispersion (2) had a viscosity of 70 cps (25”C
The emulsion remained stable, with no sedimentation of the dispersed particles or separation of the polysiloxane, even after the emulsion was allowed to stand for a week using a B-type viscometer, 60 rpm). In addition, the remaining ethyl alcohol and toluene are 230PP dust and 870pp■, respectively.
Met.

Reference Example 3 In a fourth flask similar to that used in Reference Example 1, a polysiloxane having an average molecular weight of 4 was added as a polysiloxane containing terminal hydroxyl groups.
3 parts of 8000% linear dihydroxydimethylpolysiloxane and 100 parts of toluene were charged, and under a nitrogen atmosphere,
The temperature was raised to 80°C.

A homogeneous monomer solution consisting of 30 parts of methyl methacrylate, 30 parts of styrene, 25 parts of vinyl acetate, 10 parts of acrylic acid, 5 parts of 2-styrylethyltrimethoxysilane and 2 parts of azobisisobutyronitrile was added to this. , Reference example 1
The same initial polymerization operation and dropwise addition operation of a homogeneous monomer solution were performed. When the polymerization was carried out for 15 minutes after the dropwise addition of the monomer homogeneous solution was completed, 100 parts of isopropyl alcohol was added to dilute the solution. The polymerization reaction was further continued at 80° C. for 3 hours and 45 minutes, and then cooled to obtain a polysiloxane graft polymer solution (hereinafter referred to as polymer solution (3)). 2 parts of 28% ammonia water was added to 200 parts of the obtained polymer solution (3) under stirring, and stirring was continued for 10 minutes.
238 parts of water was added and water-dispersed to obtain a polysiloxane graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (3)).

The obtained aqueous dispersion (3) had a viscosity of 750 cps (25°C
, B-type viscometer, 80 rpm) for -weeks M! Even after i.i., the emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane.

Reference Example 4 The amount of acrylonitrile in Reference Example 2 was increased from 20i to 5 parts,
The same operation as in Reference Example 2 was carried out except that the amount of acrylic acid was changed from 5 parts to 20 parts, and a polysiloxane graft polymer aqueous fraction (hereinafter referred to as aqueous dispersion (4)) was obtained.
I got it. The resulting aqueous dispersion (4) has a viscosity of 220 cps
(25° C., Type B viscometer, 60 rpm) The emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane even after being allowed to stand for a week. In addition, residual ethyl alcohol and toluene are each 300 ppm.
, 1100 pp amount.Reference Example 5 In place of the terminal hydroxyl group-containing polysiloxane used in Reference Example 1, a partially branched dimethylpolymer having an average of 4 terminal hydroxyl groups and an average molecular weight of 260,000 was used. A polysiloxane graft polymer aqueous dispersion (hereinafter referred to as aqueous dispersion (5)) was obtained by performing the same operation as in Reference Example 1 except for using a 30i 11% toluene solution of siloxane. The resulting aqueous dispersion (5) has a viscosity of 12
cps (25° C., Type B viscometer, 60 rpm) for a week, the emulsion remained stable without sedimentation of the dispersed particles or separation of the polysiloxane. In addition, the remaining isopropyl alcohol and toluene are each 70%
It was 800 ppm.

Comparative Reference Example 1 A comparative polymer solution (hereinafter referred to as a comparative polymer solution (1
), we got ). Obtained comparative polymer solution (+)
After diluting by adding 60 parts of inpropyl alcohol to 140 parts, 3 parts of 28% aqueous ammonia was added with stirring, and after stirring was continued for 10 minutes, 237 parts of water was added and water-dispersed to prepare an aqueous solution for comparison. Dispersion (hereinafter referred to as comparative aqueous dispersion (1)
) was obtained. When the obtained comparative aqueous dispersion (1) was stored overnight, the polysiloxane was separated into an upper layer.

Comparative Reference Example 2 The same terminal hydroxyl group-containing polysiloxane as used in Reference Example 1 was added to 302 parts of a polymer solution obtained in exactly the same manner as in Reference Example 1, except that the terminal hydroxyl group-containing polysiloxane in Reference Example 1 was not used. 10 parts of a 30% by weight toluene solution of group-containing polysiloxane were added and mixed to obtain a comparative polymer solution (hereinafter referred to as comparative polymer solution (2)). After diluting 140 parts of the obtained comparative polymer solution (2) with 60 parts of inpropyl alcohol, 3 parts of 28% aqueous ammonia was added with stirring, and after continued stirring for 10 minutes, 237 parts of water was added. and water-dispersed to obtain a comparative aqueous dispersion (hereinafter referred to as comparative aqueous dispersion (2)). The resulting comparative aqueous dispersion (2) was left to stand for one night, and the polysiloxane was separated into an upper layer.

Comparative Reference Example 3 The same operation as in Reference Example 1 was performed except that the amount of acrylic acid in Reference Example 1 was changed from 5 parts (L5 parts), and a comparative polysiloxane graft polymer aqueous dispersion (hereinafter referred to as a comparative aqueous dispersion) was prepared. When the obtained comparative aqueous dispersion (3) was allowed to stand for -1 week, the particles settled and a transparent aqueous layer was separated in the upper layer.

Comparative Reference Example 4 A four-hole flask similar to that used in Reference Example 1 was charged with 220 parts of deionized water and 1 part of a 7-ion emulsifier, and the temperature was raised to 80° C. under a nitrogen atmosphere. on the other hand.

3 parts of a polysiloxane macromer whose dimethylsiloxane moiety has a molecular weight of 10,000 and terminals are methacryloxypropyl and methyl groups, 70 parts of methyl methacrylate, 20 parts of butyl acrylate, 5 parts of acrylic acid, γ-methacryloxypropyltri A homogeneous monomer solution consisting of 5 parts of methoxysilane was prepared, and 10% by weight of this homogeneous monomer solution
A corresponding amount and 10 parts of a 10% aqueous solution of ammonium persulfate were added to the four-loaf flask, and the temperature was raised to 80° C. to carry out initial emulsion polymerization for 10 minutes. After completing the initial emulsion polymerization, the remaining monomer homogeneous solution was added dropwise over 2 hours at the same temperature, and the polymerization reaction was continued by stirring for 2 hours while maintaining the temperature at 80°C. The emulsion polymerization reaction was completed. When the comparative polysiloxane graft polymer aqueous dispersion thus obtained (hereinafter referred to as aqueous dispersion (4)) is allowed to stand, the polysiloxane component smoothly separates.
A uniform aqueous dispersion could not be obtained.

Examples 1-8 and Comparative Examples 1-5 Aqueous dispersions (1) to (5) obtained in Reference Examples 1 to 5.

Comparative aqueous dispersions (1) to (4) obtained in Comparative Reference Examples 1 to 4
) and polymer solution (1).
Add the type and amount of water-soluble resin and crosslinking agent shown in the table,
The stripping agent composition (1) of the present invention was stirred at room temperature for 15 minutes.
(8) and comparative release agent compositions (1) to (5) were prepared.

These compositions were coated on high-quality paper with a thickness of 15 #L and 10
After drying at 0° C. for 10 minutes, the coating film was left to stand at room temperature for 2 hours, and a polyester tape was applied to the adhesive tape.

After storing this at 35°C for one week, the adhesive tape was peeled off from the high-quality paper, and the peelability was evaluated by measuring the peeling force. Further, the peeled adhesive tape was pressure-bonded to a stainless steel plate, and the residual adhesive strength of the adhesive tape was measured to evaluate migration resistance. The peeling force and residual adhesive strength are expressed as the peeling force determined by a 180 degree peel test, and the peeling speed was 30 c+s/min.

The migration resistance of the release agent composition can be evaluated based on the magnitude of the residual FA adhesive strength. If the residual adhesive strength is large, delamination of the coating film will occur, but the migration resistance will be good. In addition, when the residual adhesive strength is small, delamination of the coating film (particularly, shedding of the polysiloxane component in the coating film) easily occurs, and the migration resistance is poor.

The evaluation results are shown in Table 1.

Examples 9-10 Release agent compositions (6) and (7) were applied to cellophane to a thickness of Ig and dried at 100°C for 1 minute.

Cellophane tape was pressed onto the coating film obtained by leaving it in a room for 2 hours.

The peelability and migration resistance were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Table 2 Example 11N13 Using the aqueous dispersion (5) obtained in Reference Example 5, the type and amount of water-soluble resin and crosslinking agent shown in Table 3 were added, and 1
The stripping agent compositions (8) to (11) of the present invention were stirred for 5 minutes.
adjusted.

These were applied to a polyethylene terephthalate film, dried at 100° C. for 1 minute, and a cellophane tape was pressed onto the resulting coating film.

The peelability and migration resistance were evaluated in the same manner as in Example 1, and the results are shown in Table 3.

Claims (1)

[Claims] 1. Polysiloxane containing terminal hydroxyl group (A) 1-
In the presence of 20% by weight, 0.0% of polymerizable silane compound (B)
5 to 10% by weight, unsaturated organic acid (C) 1 to 30% by weight, and other polymerizable monomers copolymerizable with these (D) 40
A polymer obtained by polymerizing ~97.95% by weight (however, the total of components (A), (B), (C), and (D) is 100% by weight) in an organic solvent other than alcohol. A stripping agent composition comprising an aqueous dispersion of a salt of a basic compound of a polysiloxane graft polymer obtained by stirring a liquid obtained by adding a basic compound and water to a solution of the above. 2. The stripping agent composition according to claim 1, wherein the aqueous dispersion of a salt of the polysiloxane graft polymer based on a basic compound further contains a water-soluble resin. 3. An aqueous dispersion of a salt of a basic compound of a polysiloxane graft polymer has a basic compound addition amount of 20 to 200 mol% of the acid groups in the polysiloxane graft polymer.
The amount of water added is 30 to 1000 parts by weight per 100 parts by weight of the polysiloxane graft polymer solution, and the amount of water-soluble organic solvent in the liquid before or after addition of water is 30-100 for the total amount of solvent
3. The stripping agent composition according to claim 1 or 2, which is obtained by adjusting the composition to % by weight. 4. Any one of claims 1 to 3, wherein the aqueous dispersion of a salt of a polysiloxane graft polymer made from a basic compound is dispersed in water and then further desolventized. The stripping agent composition according to item 1. 5. The release agent composition according to any one of claims 1 to 4, which uses a crosslinking agent in combination. 6. The water-soluble resin is 0.01 to 100 parts by weight (in terms of solid content) of the polysiloxane graft polymer aqueous dispersion.
3. A stripping agent composition according to claim 2, in a proportion of 20 parts by weight. 7.Claim 2, wherein the water-soluble resin is polyvinyl alcohol.
or 6. The stripping agent composition according to 6.