JPH06248002A - Cellulose-modified polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer excellent in heat resistance, film strength, adhesiveness etc., useful as an electrophotographic carrier or the surface modifier for plastic films, made up of a cellulose as skeletal polymer and a specific silicon-contg. copolymer as branched polymer. CONSTITUTION:This polymer is made up of a cellulose derivative such as cellulose, ethyl cellulose or nitrocellulose as skeletal polymer and as branched polymer, a copolymer from a reactive silicone oil such as a compound of formula I (R is CH3 or phenyl; (n) is 10-200) or of formula II and a vinyl monomer such as methyl acrylate, n-butyl acrylate or styrene. The polymer can be obtained by solution polymerization of 5-80wt.% of the cellulose derivative, 1-60wt.% of the silicone oil and 10-85wt.% of the vinyl monomer in a solvent such as an aromatic hydrocarbon or an ester using oil-soluble polymerization initiator such as benzoyl peroxide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention mainly imparts water repellency, lubricity, releasability, heat resistance, durability and the like to the surface of a plastic film such as polyvinyl chloride or polyester or a carrier used for electrophotography. It relates to a cellulose-modified polymer used for.

[0002]

BACKGROUND OF THE INVENTION For example, soft polyvinyl chloride for agriculture (PV
C), dustproof PVC film, etc.
Polyethylene terephthalate (PET) used for the purpose of imparting releasability and the like, for the purpose of imparting environment resistance and durability to carriers such as iron powder and ferrite used in electrophotography, or as a base material for magnetic tapes, thermal transfer ribbons, etc. In order to impart water repellency, lubricity, releasability, heat resistance and the like to the surface or back surface of a plastic film substrate such as) or polyethylene naphthalate (PEN), a film or particle surface is coated.

[Prior art]

Conventionally, reactive silicone oil has been used for coating the surface of such films and particles.

[0004]

However, in the case of the above reactive silicone oil, it is difficult to sufficiently satisfy the heat resistance required for the back coating agent of the thermal transfer ribbon, and the heat resistance is satisfied. However, on the other hand, in many cases, the film strength and adhesiveness are poor.

[0005]

[Means for Solving the Problems] As a means for solving the above-mentioned conventional problems, the present invention uses a cellulose and / or cellulose derivative A as a trunk polymer, a reactive silicone oil B and a vinyl monomer C. The present invention provides a cellulose-modified polymer characterized in that the copolymer is a branch polymer.

[Cellulose and / or Cellulose Derivative A] Cellulose and / or cellulose used in the present invention
Alternatively, as the cellulose derivative A, cellulose, nitrocellulose, cellulose acetate butyrate (CA
B), ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc., but CAB or ethyl cellulose is preferable in view of solubility in organic solvents and safety. Two or more types of the above cellulose and / or cellulose derivative may be used in combination.

[Reactive Silicon Oil B] As the reactive silicone oil B used in the present invention,

[Chemical 1] Where R: phenyl, CH ₃ , n: 10 to 200

[Chemical 2] Here, there are R: phenyl, CH ₃ , n: 10 to 200, etc., a silicon compound having a functional group such as an OH group and an epoxy group at one end, and a polydialkylsiloxane compound having a radically polymerizable unsaturated group at one end. . In the present invention, the reactive silicone oil has a molecular weight of 500 to
About 30,000 can be used.

[Vinyl Monomer C] Another vinyl monomer C used in the present invention is one that is copolymerizable with the above-mentioned cellulose and / or cellulose derivative A and the above-mentioned reactive silicone oil B, for example, Methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-
Butyl acrylate, 2-ethylhexyl acrylate,
Cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether , Iso-butyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-
Hydroxypropyl methacrylate, allyl alcohol, glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, citraconic acid, acrylamide, methacrylamide, N-methylol acrylamide, N There are vinyl monomers such as methylol methacrylamide. Two or more kinds of the above monomers may be used.

[Production of Graft Copolymer] The graft copolymer of the present invention is usually produced by solution polymerization. In the solution polymerization, toluene, aromatic hydrocarbon solvents such as xylene, acetone, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone, ethyl acetate, ester solvents such as butyl acetate, ethanol, iso-propanol, sec- An alcohol solvent such as propanol can be used alone or as a mixed solvent. In the solution polymerization, an oil-soluble polymerization initiator such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, azobisvaleronitrile or the like is used.

In the method of graft polymerizing a branch polymer onto a trunk polymer which is a cellulose and / or a cellulose derivative, there are a method of utilizing a hydrogen abstraction reaction and a method of giving a graft active site to cellulose.
In the method of (1), it is desirable to use a polymerization initiator having a strong hydrogen abstraction action in the presence of a cellulose derivative, for example, benzoyl peroxide, dicumyl peroxide,
t-butyl peroxyisopropyl carbonate, t-
Preference is given to using organic peroxides such as amyl perbenzoate, t-butyl perbenzoate, di-t-butyl peroxide, bis (t-butyl peroxyisopropyl) benzene.

Another method is disclosed in JP-A-63-18230.
No. 2 by reacting a functional group capable of reacting with a hydroxyl group of cellulose and / or a cellulose derivative, for example, a functional group of a vinyl monomer having a carboxyl group or an isocyanate group with a hydroxyl group of the cellulose and / or a cellulose derivative. A method of introducing a double bond into the cellulose derivative for grafting is effective, and as the vinyl monomer having a carboxyl group, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride is used. , Citraconic acid and the like, and the vinyl monomer having an isocyanate group includes isocyanate ethyl methacrylate and methacryloyl isocyanate. In this case, in addition to the above organic peroxides, azo-based polymerization initiators such as azobisisobutyronitrile, azobisvaleronitrile, azobisdimethylvaleronitrile and azobiscyclohexanecarbonitrile, which have a weak hydrogen abstraction action, can be used.

As a method of introducing the reactive silicone oil B into the branch polymer, a radical polymerizable silicone oil may be usually copolymerized with the vinyl monomer C by a highland method, and a hydroxyl group at the end may be used. In the case of the reactive silicone oil B having an epoxy group or the like, for example, a double bond is introduced into the reactive silicone oil B by reacting the carboxyl group-containing vinyl monomer or the isocyanate group-containing vinyl monomer. There is a method of copolymerizing with the vinyl monomer C above, or a method of reacting the reactive silicone oil B with a copolymer of the vinyl monomer C having a carboxyl group or an isocyanate group. The reaction between the hydroxyl group or epoxy group of B and the carboxyl group or isocyanate group of the vinyl monomer C is predetermined. Catalyst is used.

In synthesizing the cellulose-modified polymer of the present invention, cellulose and / or cellulose derivative A is removed from water contained in the cellulose if necessary, and the amount is 5 to 80% by weight, preferably 10 to 50% by weight. %, The reactive silicone oil B is 1 to 60% by weight, preferably about 5 to 40% by weight, and one or more of the vinyl monomers C is about 10 to 85% by weight.

[Coating] The thus obtained coating composition of the present invention is usually applied to a surface of PVC film, PET film or the like by a usual coating method such as spraying, roll coater, flow coater or spin coating to give a coating composition of 1 μm. The following film thickness is applied. The coating film obtained by the above-mentioned coating is cross-linked even when dried at room temperature, but is usually subjected to forced drying at 100 to 120 ° C for about 3 to 7 minutes.

[0015]

According to the present invention, a polymer having cellulose and / or cellulose derivative A as a backbone and polysiloxane B
The properties of the graft polymer with the branch polymer containing the vinyl monomer C and the vinyl monomer C are effectively exhibited. That is, the trunk polymer cellulose and / or cellulose derivative increases the intermolecular cohesive energy to improve the heat resistance, flexibility and adhesion of the coating film, and the branch polymer polysiloxane improves water repellency, lubricity and releasability. Etc. will be good.

[0016]

【Example】

[Example 1] (Production of cellulose-modified polymer) CAB-381-01 (trade name: cellulose acetate butyrate manufactured by Eastman Kodak Company) was placed in a 500 ml flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing tube. 20 parts by weight (hereinafter simply referred to as "parts"), 50 parts of methyl methacrylate, AK-5 (trade name of Toagosei Chemical Industry Co., Ltd .: silicon macromonomer molecular weight: about 500)
0) 30 parts, BIC-75 (trade name: Kayaku Akzo Co., Ltd .: t
-Butyl peroxyisopropyl carbonate) 0.5
And 20 parts of methyl isobutyl ketone were charged, and the temperature was adjusted to 8
After reacting at 0 ° C. for 4 hours, BIC-75 0.05
After adding a solution in which 30 parts of methyl isobutyl ketone was dissolved, the reaction was continued at 80 ° C. for 4 hours. Thus, a milky white resin liquid having a solid content of 33% by weight was obtained. This is designated as resin A.

Example 2 (Production of Cellulose Modified Polymer) N-14 (Hercules trade name: ethyl cellulose) 100 was added to a 500 ml flask equipped with a stirrer, a thermometer, a condenser, a separator and a nitrogen gas inlet tube. And 400 parts of toluene were charged and dehydration was carried out by azeotropic distillation for 4 hours. 100 parts of this dehydrated ethyl cellulose solution (solid content 20% by weight), methyl isobutyl ketone 9
After charging 0 part and 1 part of methacryloyl isocyanate and reacting for 30 minutes at room temperature to introduce an unsaturated double bond into cellulose, FM-0711 (trade name: reactive silicon manufactured by Chisso Corporation) 20 parts, methyl methacrylate 5
After charging 0 parts, 10 parts of methacrylic acid and 1 part of azobisisobutyronitrile and reacting at 80 ° C. for 4 hours, a solution of 0.05 part of azobisisobutyronitrile dissolved in 30 parts of toluene was added. After that, the mixture was further reacted at 80 ° C. for 4 hours. Thus, a pale yellow transparent resin liquid having a solid content of 33% by weight was obtained. This is designated as Resin B.

Example 3 (Production of Cellulose Modified Polymer) Dehydrated CAB-55 obtained in the same manner as in Example 2.
170 parts of a 20% by weight methyl isobutyl ketone solution of 3-04 (trade name: cellulose acetate butyrate manufactured by Eastman Kodak Co., Ltd.), methyl methacrylate 40
Parts, methacrylic acid 10 parts, methyl isobutyl ketone 40
And 1 part of benzoyl peroxide were charged and reacted at 100 ° C. for 4 hours, then benzoyl peroxide 0.05
After adding a solution in which 30 parts of methyl isobutyl ketone was dissolved, the reaction was continued at 80 ° C. for 4 hours. To this solution, 10 parts of reactive silicone oil (molecular weight 1000) having the following structural formula was charged, 0.5 part of tetramethylammonium chloride was added as a catalyst, and the mixture was reacted at 90 ° C. for 8 hours to reduce acid value and NMR. It was confirmed that silicone oil was introduced into the resin skeleton. Thus, a resin liquid having a solid content of 34% by weight was obtained. This is designated as Resin C.

[Chemical 3]

Comparative Example 1 (Production of Comparative Polymer D) 50 parts of methyl methacrylate was prepared in the same apparatus as in the Example.
FM-0725 (manufactured by Chisso Corporation, trade name: reactive silicone oil, molecular weight 10000) 30 parts, butyl acrylate 10 parts, methacrylic acid 10 parts, methyl ethyl ketone 170 parts, azobisisobutyronitrile 1 part, except that the same operation. To obtain a milky white resin liquid having a solid content of 33% by weight. This is designated as resin D.

[Comparative Example 2] (Production of Comparative Polymer E) Synthesis was carried out according to the same composition and procedure except that the polymerization initiator was changed to azobisisobutyronitrile in Example 1, and the solid content was 33% by weight. To obtain an opaque resin liquid. This is designated as resin E.

Comparative Example 3 (Production of Comparative Polymer F) 100 parts of the dehydrated ethyl cellulose solution used in Example 2 and 300 parts of Resin D synthesized in Comparative Example 1 were mixed to prepare a resin liquid. The solid content is 30% by weight and the resin F
And

Examples 1 to 3 and Comparative Examples 1, 2, 3
Each of the copolymers A, B, C, D, E, and F obtained by the above procedure was adjusted to a solid content of 5% by weight with methyl ethyl ketone, and the above samples were each applied to a PET film by a roll coater to give a film thickness of 0. After coating to have a thickness of 5 μm and forced drying at 115 ° C. for 5 minutes, a test for physical properties was performed. The results are shown in Table 1.

[0023]

[Table 1] Test method Adhesion: Cross-cut cellophane tape peeling test Dynamic friction coefficient: HEIDON-type friction measuring device Membrane strength: Lesca scratch tester Ts (° C): Thermal softening point by a thermo-mechanical analyzer by Seiko Denshi

According to Table 1, Samples 1, 2, and 3 using the cellulose-modified polymer of the present invention have good lubricity (dynamic friction coefficient), adhesion, film strength, and thermal softening temperature (Ts). However, Comparative Sample 1, which was not modified with cellulose, was inferior in adhesion, film strength, and thermal softening temperature. Further, in the case of Comparative Sample 2, since azobisisobutyronitrile, which has a weak hydrogen abstraction action even when cellulose is used, is used as an initiator, graft polymerization with cellulose is insufficient, and adhesion and lubricity are good. However, the film strength was poor and there were two peaks at the softening point. Further, in this comparative sample 2, the resin liquid was separated when left for one week at room temperature. Further, in Comparative Sample 3, the coated film was opaque and was not tested.

[0025]

Therefore, in the present invention, by modifying with cellulose, a resin composition satisfying the lubricity, water repellency and releasability of silicone, and having excellent adhesion, heat resistance and film strength can be obtained. .

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[Procedure amendment]

[Submission date] April 23, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title of the invention Cellulose modified polymer

[Claims]

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention mainly imparts water repellency, lubricity, releasability, heat resistance, durability and the like to the surface of a plastic film such as polyvinyl chloride or polyester or a carrier used for electrophotography. It relates to a cellulose-modified polymer used for.

[0002]

BACKGROUND OF THE INVENTION For example, soft polyvinyl chloride for agriculture (PV
C) The purpose of imparting dust resistance, barrier properties, peelability, etc. to films , dust-proof PVC films, etc., the purpose of imparting environment resistance and durability to carriers such as iron powder and ferrite used in electrophotography, or magnetic properties. Polyethylene terephthalate (P, used as a base material for tapes, thermal transfer ribbons, etc.
ET) or polyethylene naphthalate (PEN) or other plastic film base material is coated on the surface of the film or particles for the purpose of imparting water repellency, lubricity, releasability, heat resistance, etc. .

[0003]

2. Description of the Related Art Conventionally, reactive silicone oil has been used for the surface coating of such films and particles.

[0004]

However, in the case of the above reactive silicone oil, it is difficult to sufficiently satisfy the heat resistance required for the back coating agent of the thermal transfer ribbon, and the heat resistance is satisfied. However, on the other hand, in many cases, the film strength and adhesiveness are poor.

[0005]

[Means for Solving the Problems] As a means for solving the above-mentioned conventional problems, the present invention uses a cellulose and / or cellulose derivative A as a trunk polymer, a reactive silicone oil B and a vinyl monomer C. there is provided a cellulose-modified polymer obtained by the branch polymer a copolymer.

[Cellulose and / or Cellulose Derivative A] Cellulose, nitrocellulose, cellulose acetate butyrate (C
AB), ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc., but CAB or ethyl cellulose is preferable in view of solubility in organic solvents and safety. Two or more types of the above cellulose and / or cellulose derivative may be used in combination.

[Reactive Silicon Oil B] As the reactive silicone oil B used in the present invention,

[Chemical 1] Where R: phenyl, CH ₃ , n: 10 to 200

[Chemical 2] Here, there are R: phenyl, CH ₃ , n: 10 to 200, etc., a silicon compound having a functional group such as an OH group and an epoxy group at one end, and a polydialkylsiloxane compound having a radically polymerizable unsaturated group at one end. . In the present invention, the reactive silicone oil has a molecular weight of 500 to
About 30,000 can be used.

[Vinyl Monomer C] Another vinyl monomer C used in the present invention is one that is copolymerizable with the above-mentioned cellulose and / or cellulose derivative A and the above-mentioned reactive silicone oil B. Methyl acrylate, ethyl acrylate, n-butyl acrylate, is
o-Butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether , N-propyl vinyl ether, n-butyl vinyl ether, iso-butyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride,
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate, allyl alcohol, glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, citraconic acid, acrylamide, methacrylamide, N-methylolacrylamide , Vinyl monomers such as N-methylolmethacrylamide. Two or more kinds of the above monomers may be used.

[0009] Production of graft copolymer] cell of the present invention
The lulose-modified polymer is usually produced by solution polymerization. In the solution polymerization, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ethanol, a
Seo alcohol solvent such as propanol may be used alone or as a mixed solvent. In the solution polymerization, an oil-soluble polymerization initiator such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, azobisisobutyronitrile, azobisvaleronitrile or the like is used.

In the method of graft-polymerizing a branch polymer on a trunk polymer which is cellulose and / or a cellulose derivative, there are a method of utilizing a hydrogen abstraction reaction and a method of giving a grafting active point to cellulose.
In the above method, it is desirable to use a polymerization initiator having a strong hydrogen abstraction action in the presence of a cellulose derivative, for example, benzoyl peroxide, dicumyl peroxide, t-butylperoxyisopropyl carbonate,
Preference is given to using organic peroxides such as t-amyl perbenzoate, t-butyl perbenzoate, di-t-butyl peroxide, bis (t-butyl peroxyisopropyl) benzene.

Another method is disclosed in JP-A-63-1823.
No. 02 by reacting a functional group capable of reacting with a hydroxyl group of cellulose and / or a cellulose derivative, for example, a functional group of a vinyl monomer having a carboxyl group or an isocyanate group with a hydroxyl group of the cellulose and / or a cellulose derivative. A method of introducing a double bond into the cellulose derivative for grafting is effective, and as the vinyl monomer having a carboxyl group, there are acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and the like , Examples of the vinyl monomer having an isocyanate group include isocyanate ethyl methacrylate and methacryloyl isocyanate. In this case, in addition to the above organic peroxides, azo-based polymerization initiators such as azobisisobutyronitrile, azobisvaleronitrile, azobisdimethylvaleronitrile and azobiscyclohexanecarbonitrile, which have a weak hydrogen abstraction action, can be used.

As a method for introducing the reactive silicone oil B into the branch polymer, a radically polymerizable silicone oil may be copolymerized with the vinyl monomer C by a generally known method, and a terminal hydroxyl group may be used. In the case of the reactive silicone oil B having an epoxy group or the like, for example, a double bond is introduced into the reactive silicone oil B by reacting the carboxyl group-containing vinyl monomer or the isocyanate group-containing vinyl monomer. There is a method of copolymerizing with the vinyl monomer C above, or a method of reacting the reactive silicone oil B with a copolymer of the vinyl monomer C containing a carboxyl group or an isocyanate group. The reaction between the hydroxyl group or epoxy group of oil B and the carboxyl group or isocyanate group of vinyl monomer C is not possible. Certain catalysts may be used .

When synthesizing the cellulose-modified polymer of the present invention, the water content of the cellulose and / or the cellulose derivative A is removed if necessary, and the water content is 5 to 80% by weight, preferably 10 to 50% by weight. %
The reactive silicone oil B is about 1 to 60% by weight, preferably about 5 to 40% by weight, and one or more kinds of the vinyl monomer C is about 10 to 85% by weight.

[Coating] The coating composition of the present invention thus obtained is, for example, PVC film or PET.
A film having a thickness of 1 μm or less is usually applied to the surface of a film or the like by an ordinary coating method such as spraying, a roll coater, a flow coater, and spin coating. The coating film obtained by the coating also can dry at room temperature drying
That is, usually carried out forced drying of about 1 to 5 minutes at 100 to 120 ° C..

[0015]

According to the present invention, a polymer having cellulose and / or cellulose derivative A as a backbone and polysiloxane B
The properties of the graft polymer with the branch polymer containing the vinyl monomer C and the vinyl monomer C are effectively exhibited. That is, the trunk polymer cellulose and / or cellulose derivative increases the intermolecular cohesive energy to improve the heat resistance, flexibility and adhesion of the coating film, and the branch polymer polysiloxane improves water repellency, lubricity and releasability. Etc. will be good.

[0016]

EXAMPLES Example 1 (cellulose production of the modified copolymer) stirrer, a thermometer, a condenser, CAB-381-01 (Eastman Kodak Co. trade name flask 500ml equipped with a nitrogen gas inlet tube : 20 parts by weight of cellulose acetate butyrate) (hereinafter simply referred to as "part"), 50 parts of methyl methacrylate, AK-5 (manufactured by Toagosei Chemical Industry Co., Ltd., trade name: silicon macromonomer, molecular weight: about 5)
000) 30 parts, BIC-75 (trade name: t-butylperoxyisopropyl carbonate manufactured by Kayaku Akzo Co., Ltd.)
Charge 0.5 parts and 20 parts of methyl isobutyl ketone ,
After reacting at 0 ° C. for 4 hours, BIC-75 0.05
After adding a solution in which 30 parts of methyl isobutyl ketone was dissolved, the reaction was continued at 80 ° C. for 4 hours. Thus, a milky white resin liquid having a solid content of 33% by weight was obtained. This is designated as resin A.

Example 2 (Production of Cellulose Modified Copolymer) N-14 (Hercules trade name: ethyl cellulose) was placed in a 500 ml flask equipped with a stirrer, thermometer, condenser, separator, and nitrogen gas inlet tube. 100 parts and 400 parts of toluene were charged and dehydration operation by azeotropic distillation was performed for 4 hours. 100 parts of this dehydrated ethyl cellulose solution (solid content 20% by weight), methyl isobutyl ketone 9
After charging 0 part and 1 part of methacryloyl isocyanate and reacting at room temperature for 30 minutes to introduce an unsaturated double bond into cellulose, FM-0711 (trade name of Chisso Corporation: reactive silicone molecular weight 1000 ) 20 parts, A solution prepared by charging 50 parts of methyl methacrylate, 10 parts of methacrylic acid and 1 part of azobisisobutyronitrile, reacting at 80 ° C. for 4 hours, and then dissolving 0.05 parts of azobisisobutyronitrile in 30 parts of toluene. 8 more after adding
The reaction was carried out at 0 ° C for 4 hours. In this way, the solid content 33
A pale yellow transparent resin liquid of weight% was obtained. This is designated as Resin B.

Example 3 (Production of Cellulose Modified Copolymer) Dehydrated CAB-55 obtained in the same manner as in Example 2.
3-04 (Eastman Kodak Corporation, trade name: cellulose acetate butyrate) 170 parts of 20 wt% methyl isobutyl ketone solution, methyl methacrylate 40
Parts, methacrylic acid 10 parts, methyl isobutyl ketone 40
And 1 part of benzoyl peroxide were charged and reacted at 100 ° C. for 4 hours, then benzoyl peroxide 0.05
A solution in which 30 parts of methyl isobutyl ketone was dissolved was added, and the mixture was further reacted at 80 ° C. for 4 hours. Reactive silicone oils having the following structural formula to the resin solution (molecular weight:
000) was charged in an amount of 10 parts, 0.5 parts of tetramethylammonium chloride as a catalyst was added, and the mixture was reacted at 90 ° C. for 8 hours to reduce the acid value and confirmed by NMR that silicon oil was introduced into the resin skeleton. Thus, a resin liquid having a solid content of 34% by weight was obtained. This is designated as Resin C.

[Chemical 3]

[0019] Comparative Example 1 (Comparative Preparation of polymer D) Example similar device dice chill methacrylate 50 parts, F
M-0725 (manufactured by Chisso Corporation, trade name: reactive silicone oil, molecular weight 10,000), 30 parts, butyl acrylate, 10 parts, methacrylic acid, 10 parts, methyl ethyl ketone, 170 parts, and azobisisobutyronitrile, 1 part. To obtain a milky white transparent resin liquid having a solid content of 32.6 % by weight. This is designated as resin D.

[Comparative Example 2] (Production of Comparative Polymer E) Synthesis was carried out according to the same composition and procedure except that the polymerization initiator was changed to azobisisobutyronitrile in Example 1, and the solid content was 33% by weight. To obtain an opaque resin liquid. This is designated as resin E.

Comparative Example 3 (Production of Comparative Polymer F) 100 parts of the dehydrated ethyl cellulose solution used in Example 2 and 300 parts of Resin D synthesized in Comparative Example 1 were mixed to prepare a resin liquid. The solid content is 30% by weight and the resin F
And

Examples 1 to 3 and Comparative Examples 1, 2, 3
Each of the copolymers A, B, C, D, E, and F obtained by the above procedure was adjusted to a solid content of 5% by weight with methyl ethyl ketone, and the above samples were each applied to a PET film by a roll coater to give a film thickness of 0. After coating to have a thickness of 5 μm and forced drying at 115 ° C. for 5 minutes, a test for physical properties was performed. The results are shown in Table 1.

[0023]

[Table 1] Test method Adhesion: Cross-cut cellophane tape peeling test Dynamic friction coefficient: HEIDON type friction measuring device Membrane strength: Lesca scratch tester Ts : Seiko Denshi thermomechanical analyzer thermal softening point

According to Table 1, Samples 1, 2, and 3 using the cellulose-modified polymer of the present invention have good lubricity (dynamic friction coefficient), adhesion, film strength, and thermal softening temperature (Ts). However, Comparative Sample 1, which was not modified with cellulose, was inferior in adhesion, film strength, and thermal softening temperature. Further, in the case of Comparative Sample 2, since azobisisobutyronitrile, which has a weak hydrogen abstraction action even when cellulose is used, is used as an initiator, graft polymerization with cellulose is insufficient, and adhesion and lubricity are good. However, the film strength was poor and there were two peaks in the thermal softening point. Further, in this comparative sample 2, the resin liquid was separated when left for one week at room temperature. Further, in Comparative Sample 3, the coated film was opaque and was not tested.

[0025]

Effect of the Invention] Accordingly, lubricity possessed by the silicone by modifying the cellulose in the present invention, water repellency, satisfying releasability and adhesion, heat resistance, a resin composition excellent in film strength can give To be

Front page continued (72) Inventor Susumu Kawakami 8-3 Ninomachi, Mizuho-ku, Nagoya, Aichi Natco Paint Co., Ltd. (72) Hironori Hata 8-3 Nino-cho, Mizuho-ku, Nagoya, Aichi Natco Paint Co., Ltd. (72) Inventor Keiji Taniguchi 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh Company (72) Inventor Shigeyuki Harada 1-3-6 Nakamagome, Ota-ku, Tokyo Share Company Ricoh

Claims (1)

[Claims] 1. A cellulose-modified polymer comprising cellulose and / or cellulose derivative A as a trunk polymer and a copolymer of reactive silicone oil B and vinyl monomer C as a branch polymer.