JPH0881520A - Production of resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin compsn. improved in compatibility and clarity by saponifying a vinyl ester polymer in the presence of a specific polymer. CONSTITUTION: A polymer having a double bond at one molecular end iis reacted with 1/3-10 equivalents (based on 1 equivalent of double bonds of the polymer) of a boron complex and 1-100 equivalents (based on 1 equivalent of double bonds of the polymer) of a trialkoxyborane in a nitrogen atmosphere at room temp. to 300 deg.C for 1min to 10hr to give a polymer which has a mol.wt. of 50-100,000 and has, at one molecular end, a functional group selected from among a boronic acid group, a borinic acid group, and a group convertible into a boronic or borinic acid group in the presence of water. 100 pts.wt. vinyl ester polymer is saponified in the presence of 1-100 pts.wt. polymer above-obtd. and 1-100 milliequivalents of an alkali or acid catalyst in a solvent at 10-130 deg.C for 5min to 3hr, giving a resin compn. having a degree of saponification of 40-100mol% and a viscosity-average degree of polymn. of 50-30,000.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a resin composition having excellent compatibility and transparency.

[0002]

2. Description of the Related Art Polyvinyl alcohol polymer (hereinafter referred to as P
(Abbreviated as VA) is excellent in film-forming property, transparency and strength, and therefore, it is a paper modifier such as a coating agent for paper and an internal additive for paper, an adhesive agent for paper, wood and inorganic substances, It is used in a wide range of applications including molded products such as warp sizing agents, various films and sheets. The flexibility of PVA changes with temperature and humidity, and it becomes hard and brittle or soft and supple depending on the surrounding environment. In order to control this property, a method of blending a plasticizer or a polymer other than PVA has been used. However, when a plasticizer is added, there is a problem that its content decreases with time. Further, when PVA and a polymer other than PVA are blended, there is a problem that mechanical properties are significantly reduced or transparency is significantly reduced due to poor compatibility between the two.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition containing PVA as one component, which is excellent in compatibility and transparency.

[0004]

[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, as a result, a boronic acid group, a borinic acid group, and a boron-containing group which can be converted into a boronic acid group or a borinic acid group in the presence of water are formed. The present invention has been completed by finding a method for producing a resin composition, which comprises saponifying a vinyl ester polymer (B) in the presence of a polymer (A) having a functional group selected from the group at one end. Came to.

Polymers used in the present invention having at one end a functional group selected from the group consisting of boronic acid groups, borinic acid groups and boronic acid groups or boron-containing groups which can be converted into boric acid groups in the presence of water. (A) means a boronic acid group, a borinic acid group, and a boron-containing group that can be converted into a boronic acid group or a borinic acid group in the presence of water, at one terminal of the polymer (preferably one group by a boron-carbon bond). It is a polymer bound to only the ends). In the present invention, the boronic acid group means the following chemical formula 1
It is shown by.

[0006]

Embedded image

The boron-containing group which can be converted to a boronic acid group in the presence of water (hereinafter simply referred to as a boron-containing group) is hydrolyzed in the presence of water and is represented by the chemical formula 1 above. Any boron-containing group that can be converted into an acid group may be used, and typical examples thereof include a boronic acid ester group represented by the following chemical formula 2, a boronic acid anhydride represented by the following chemical formula 3, and a chemical formula 4 below. Boronic acid bases may be mentioned.

[0008]

Embedded image

[0009]

[Chemical 3]

[0010]

[Chemical 4]

{In the formula, X and Y are hydrogen atoms and have 1 to 2 carbon atoms.
0 aliphatic hydrocarbon group (linear or branched alkyl group, alkenyl group, etc.), alicyclic hydrocarbon group (cycloalkyl group, cycloalkenyl group, etc.), aromatic hydrocarbon group (phenyl group, biphenyl) Group),
X and Y may be the same group or different. Further, X and Y may be bonded. However, it is excluded when both X and Y are hydrogen atoms. The R ^1, R ^2, R ³ represents the X, Y and similar hydrogen atom, an aliphatic hydrocarbon group, alicyclic hydrocarbon group, an aromatic hydrocarbon group, R ^1, R ^2,
R ³ may be the same group or different. Also M
Represents an alkali metal or an alkaline earth metal. Further, the above X, Y, R ¹ , R ² and R ³ may have other groups such as a carboxyl group and a halogen atom. }

Specific examples of the boronic acid ester group represented by the above Chemical Formulas 2 to 4 include boronic acid dimethyl ester group,
Boronic acid diethyl ester group, boronic acid dipropyl ester group, boronic acid diisopropyl ester group, boronic acid dibutyl ester group, boronic acid dihexyl ester group,
Boronic acid dicyclohexyl ester group, boronic acid ethylene glycol ester group, boronic acid propylene glycol ester group (boronic acid 1,2-propanediol ester group, boronic acid 1,3-propanediol ester group), boronic acid trimethylene glycol ester group , Boronic acid neopentyl glycol ester group, boronic acid catechol ester group, boronic acid glycerin ester group,
A boronic acid ester group such as a boronic acid trimethylolethane ester group; a boronic acid anhydride group; an alkali metal base of boronic acid, an alkaline earth metal base of boronic acid and the like. Further, in the present invention, the borinic acid group is represented by the following chemical formula 5.

[0013]

[Chemical 5]

Further, the boron-containing group which can be converted into a borinic acid group in the presence of water is a boron-containing group which is hydrolyzed in the presence of water and can be converted into a borinic acid group represented by the above chemical formula 5. The representative examples thereof include a borinic acid ester group represented by the following chemical formula 6, a borinic acid anhydride represented by the following chemical formula 7, and a borinic acid base represented by the following chemical formula 8.

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

Embedded image

{In the formula, X has the same meaning as X in the above chemical formula 2, Z is an aliphatic hydrocarbon group similar to the above X,
It represents an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an amino group or an amide group. Further, X and Z may be bonded. Also,
R1, R2, R3, and M are R ¹ in the above formula 4,
It has the same meaning as R ² , R ³ and M. }

Specific examples of the borinic acid ester group represented by the above chemical formulas 6 to 8 are methyl group, ethyl group, propyl group, butyl group and 1-methyl for X, Z, R ¹ , R ² and R ^3. Examples thereof include those showing lower hydrocarbon groups such as propyl group, pentyl group, hexyl group and phenyl group. Examples thereof include a methylborinic acid group, a methylborinic acid methyl ester group, an ethylborinic acid methyl ester group, a methylborinic acid ethyl ester group, a butylborinic acid methyl ester group, and a 3-methyl-2butylbutylborinic acid methyl ester group. Among the above functional groups, a boronic acid ester group such as a boronic acid ethylene glycol ester group is particularly preferable from the viewpoint of compatibility with PVA. The boron-containing group that can be converted into a boronic acid group or a borinic acid group in the presence of water is
Polymer (A) in water or a mixed liquid of water and an organic solvent (toluene, xylene, acetone, etc.), reaction time 10
It means a group which can be converted into a boronic acid group or a borinic acid group when hydrolyzed under the conditions of a reaction temperature of room temperature to 150 ° C. for minutes to 2 hours.

The polymer (A) of the present invention has a functional group selected from the group consisting of a boronic acid group, a borinic acid group, and a boronic acid group or a boron-containing group which can be converted into a boric acid group in the presence of water. There is no particular limitation as long as it is a polymer having a terminal, but specific examples thereof include a methacrylic acid ester-based polymer, an aromatic vinyl-based polymer, an acrylamide-based polymer,
Examples thereof include a methacrylamide polymer, an N-vinylamide polymer, an oxyalkylene polymer, a vinyl ester polymer, a vinyl cyanide polymer, a vinyl halide polymer, and a vinyl ether polymer.

As the monomers constituting these polymers, methacrylic acid and its salts, methyl methacrylate,
Methacrylic acids such as ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, n-dodecyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, monoglycerin methacrylate; styrene, α-methylstyrene, t-butylstyrene. , Vinylnaphthalene and other aromatic vinyls; acrylamide, N-alkylacrylamide such as N-isopropylacrylamide, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof Acrylamides such as quaternary salts; N-alkylmethacrylamides such as methacrylamide, N-isopropylmethacrylamide, N, N-dimethylmethacrylamide, 2 Methacrylamides such as methacrylamidopropanesulfonic acid or its salts, methacrylamidopropyldimethylamine or its acid salts or its quaternary salts; N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide; Oxyalkylenes such as oxyethylene, oxypropylene, oxytetramethylene; vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate, vinyl pivalate; vinyl cyanides such as acrylonitrile and methacrylonitrile;
Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether,
Examples thereof include vinyl ethers such as butyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, methoxyethyl vinyl ether and the like.

The molecular weight of the polymer (A) is not particularly limited, but is preferably 50 to 100,000, more preferably 100 to 50,000.

Next, a typical method for producing the polymer (A) having a functional group selected from the group consisting of a boronic acid group, a borinic acid group and a boron-containing group used at the present invention at one end will be described.

First production method: A polymer having a boronic acid group, a borinic acid group or a boron-containing group at one end is reacted with a borane complex and a trialkyl borate ester to a polymer having a double bond at one end. Obtained by The introduction of the boronic acid group is carried out by reacting a polymer having a double bond at one end, a borane complex, a trialkyl borate ester and a solvent of these three components under heating in a nitrogen atmosphere while stirring. . As the borane complex, borane-tetrahydrofuran complex, borane-dimethylsulfide complex, borane-pyridine complex, borane-trimethylamine complex, borane-trimethylamine complex and the like are preferable. The amount of the borane complex charged is preferably in the range of 1/3 equivalent to 10 equivalents with respect to the double bond of the polymer. As the boric acid trialkyl ester, boric acid lower alkyl ester such as trimethyl borate, triethyl borate, tripropyl borate, and tributyl borate is preferable. The amount of the trialkyl borate ester charged is preferably in the range of 1 equivalent to 100 equivalents with respect to the double bond of the polymer. The reaction temperature is preferably room temperature to 300 ° C, and 100 to 2
50 ° C. is more preferable. The reaction time is preferably 1 minute to 10 hours, more preferably 5 minutes to 5 hours.
The types of boronic acid groups or boron-containing groups can be easily interconverted in the presence of water or alcohol. For example, boronic acid dimethyl ester becomes boronic acid by reacting with water, and boronic acid becomes ethylene glycol ester by reacting with ethylene glycol.

Second method: A polymer having a boronic acid group, a borinic acid group or a boron-containing group at one end is radically polymerized with a radically polymerizable monomer in the presence of a thiol having the boron-containing group. It can also be obtained. A thiol having a boronic acid group or a boron-containing group as a raw material can be obtained by reacting a thiol having a double bond with a diborane or borane complex in a nitrogen atmosphere, and then adding an alcohol or water. The thiol having a borinic acid group or a boron-containing group can be obtained by reacting a thiol having a double bond, a diborane or a borane complex and an olefin in a nitrogen atmosphere, and then adding an alcohol or water. Here, the thiol having a double bond is 2-propene-1-thiol, 2
-Methyl-2-propene-1-thiol, 3-butene-
1-thiol, 4-pentene-1-thiol and the like can be mentioned, of which 2-propene-1-thiol and 2-methyl-2-propen-1-thiol are preferred. As the borane complex, the same ones as described above are used, and among them, the borane-tetrahydrofuran complex is particularly preferable. The amount of diborane or borane complex added is preferably about the same as the amount of the thiol having a double bond. The reaction conditions are preferably room temperature to 200 ° C. Examples of the solvent include ether solvents such as tetrahydrofuran (THF) and diglyme; saturated hydrocarbon solvents such as hexane, heptane, ethylcyclohexane, decalin and the like. Of these, THF is preferable. As alcohols added after the reaction, lower alcohols such as methanol and ethanol are preferable, and methanol is particularly preferable. The olefins added when producing a thiol having a borinic acid group are not particularly limited, but ethylene, propylene, 1-
Butene, 2-butene, 1-pentene, 2-pentene, 2
-Methyl-1-butene, 2-methyl-2-butene, 1-
Lower olefins such as hexene and cyclohexene are preferred.

The radical polymerization in the presence of the thiol having a boronic acid group, a borinic acid group or a boron-containing group thus obtained can be carried out by a usual method. As the polymerization conditions, an azo-based or peroxide-based initiator is used,
The polymerization temperature is preferably in the range of room temperature to 150 ° C. The addition amount of the thiol having a functional group is preferably about 0.001 to 1 mmol per 1 g of the monomer, and the addition method of the thiol is not particularly limited, but the monomer such as vinyl acetate and styrene is used. When using a chain transfer-prone substance, it is preferable to add thiol sequentially during polymerization, and when using a chain-transfer-resistant substance such as methyl methacrylate, it is preferable to add a thiol from the beginning.

Examples of the vinyl ester-based polymer (B) of the present invention include homopolymers and copolymers of vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate and vinyl pivalate.

Further, the vinyl ester polymer (B) of the present invention may be copolymerized with another unsaturated monomer copolymerizable with the vinyl ester as long as the effect of the present invention is not impaired. Examples of the unsaturated monomer include olefins such as ethylene, propylene, 1-butene and isobutene; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and maleic anhydride, or salts thereof. Mono- or dialkyl esters having 1 to 18 carbon atoms; acrylamide, N-alkyl acrylamide having 1 to 18 carbon atoms, N, N-dimethyl acrylamide,
Acrylamides such as 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof; methacrylamide, N-alkylmethacrylamide having 1 to 18 carbon atoms, N, N-dimethylmethacrylamide. , Methacrylamides such as 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof; N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide or the like. Vinyl amides; allyl compounds such as allyl acetate, allyl chloride and allyl alcohol 8-hydroxy-1-octene; vinyl cyanides such as acrylonitrile and methacrylonitrile; alkyl vinyl ethers having 1 to 18 carbon atoms Hydroxyalkyl vinyl ethers, alkoxyalkyl vinyl ethers such as alkyl vinyl ethers; vinyl chloride, vinylidene chloride, vinyl fluoride,
Examples thereof include vinyl halides such as vinylidene fluoride.

The degree of polymerization of the vinyl ester polymer (B) is not particularly limited, but the viscosity average degree of polymerization of PVA obtained by completely saponifying the polymer (hereinafter abbreviated as the degree of polymerization).
50 to 30,000 is preferable, and 50 to 10,000
Is more preferable, and 100 to 5000 is particularly preferable. The method for saponifying the vinyl ester polymer (B) in the presence of the polymer (A) having a functional group selected from the group consisting of a boronic acid group, a borinic acid group and a boron-containing group at one end is not particularly limited. However, a conventional method of saponification by a transesterification reaction using an alkali catalyst or an acid catalyst and / or a direct saponification reaction is used.

The blending amount of the polymer (A) with respect to 100 parts by weight of the vinyl ester polymer (B) is preferably in the range of 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, and 5 to 50 parts by weight. Even more preferable. As the solvent, methanol, ethanol, butanol, allyl alcohol, alcohol solvent such as benzyl alcohol alone,
Alternatively, the alcoholic solvent and benzene, toluene,
A mixed solvent with an aromatic solvent such as chlorobenzene, an ether solvent such as tetrahydrofuran or dioxane, a solvent selected from acetone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone is used. The concentration of the vinyl ester polymer in the solvent is preferably in the range of 1 to 70% by weight. As the saponification catalyst, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alcoholates such as sodium methylate, sodium ethylate and potassium methylate, alkali catalysts such as amines, benzenesulfonic acid, An acid catalyst such as toluenesulfonic acid may be used. The amount of the catalyst used is preferably 1 to 1000 mmole equivalent to the vinyl ester polymer. The saponification reaction temperature is not particularly limited, but is preferably 10 to 130 ° C, more preferably 30 to 80 ° C. The reaction is usually performed for 5 minutes to 3 hours. The saponification degree of the polymer (B) after the saponification reaction is preferably 40 to 100 mol%, more preferably 60 to 100 mol%.

[0031]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, "%" and "parts" mean "% by weight" and "parts by weight", respectively, unless otherwise specified. The degree of polymerization of the polymer (B) in the examples is such that the polymer is completely saponified and JIS-K-6 is used.
726. The amount of boronic acid groups in the polymer (A) and the degree of saponification of the PVA-based polymer in the resin composition after saponification were quantified by 270 MHz- ¹ H NMR. A Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) was used for melt-kneading at 80 rpm for 10 minutes. The surface electric resistance of the film was measured by controlling the electric resistance of the film at 20 ° C. and 65% RH for 1 week, and measuring the electric resistance (HEWLETT PACKA
RD).

Synthesis Example 1 Synthesis of polyethylene glycol having a boronic acid group at one end; polyethylene glycol monoallyl ether having an average molecular weight of 350 (Uniox PKA-5006; NOF CORPORATION) was placed in a separable flask equipped with a condenser and a dropping funnel. )) Was charged and the atmosphere was replaced with nitrogen. 0 ° C
With borane-dimethyl sulfide complex 11.44 parts
The mixture was added dropwise over a period of 40 minutes, reacted for 40 minutes, heated to 40 ° C., and reacted for 3 hours. Cool to 0 ° C and methanol 1
6 parts was added dropwise over 30 minutes. Methanol and dimethyl sulfide were distilled off, and 200 parts of toluene was added.
The precipitated solid content was filtered off, and the toluene was distilled off to obtain polyethylene glycol having a boronic acid group of 2.6 meq / g at one end.

Synthesis Example 2 Synthesis of ethylene oxide-propylene oxide copolymer having a boronic acid group at one end; ethylene oxide-propylene oxide having an allyl group at one end and an average molecular weight of 1600 in a separable flask equipped with a condenser and a dropping funnel. 150 parts of a copolymer (Unisafe PKA-5015; manufactured by NOF CORPORATION, molar ratio EO / PO = 75/25) and 200 parts of toluene were charged and the atmosphere was replaced with nitrogen.
At 0 ° C., 8.01 parts of borane-dimethyl sulfide complex was added to 3 parts.
The mixture was added dropwise over 0 minutes, reacted for 40 minutes, heated to 40 ° C., and reacted for 3 hours. After cooling to 0 ° C., 8 parts of methanol was added dropwise over 30 minutes. Methanol and dimethyl sulfide were distilled off, the precipitated solid content was filtered off, and toluene was distilled off to obtain an ethylene oxide-propylene oxide copolymer having a boronic acid group at one end of 0.56 meq / g. .

Synthesis Example 3 Synthesis of 3-mercaptopropylboronic acid ethylene glycol ester (MPBE); sodium borohydride (NaBH4) 1 in a flask equipped with a condenser and a dropping funnel.
9.26 parts were charged and the atmosphere was replaced with nitrogen. THF4 which was dried with benzophenone and sodium metal and distilled
After charging 50 parts and cooling to 0 ° C. in an ice bath, boron trifluoride-diethyl ether complex 9 was stirred while stirring.
9.95 parts was added dropwise over 30 minutes. 2 hours later 0 ° C
Then, 45.61 parts of 2-propene-1-thiol was added dropwise over 30 minutes. After stirring for 40 minutes, the temperature was raised to 60 ° C. and stirring was further performed for 3 hours. Cool to 0 ° C and methanol 8
0 part was added dropwise over 40 minutes. After the reaction solution was filtered to remove the solid content, the solvent was distilled off, and ethylene glycol 38
Part of the mixture was extracted with methylene chloride-water to remove excess ethylene glycol, dried over magnesium sulfate, and then distilled under reduced pressure to give 3-mercaptopropylboronic acid ethylene glycol ester and 2-mercapto-1-methylethylboronic acid ethylene glycol ester. A 4: 1 mixture was obtained {boiling point 70 ° C. (4 mmHg)}.

Synthesis Example 4 Synthesis of polymethylmethacrylate having a boronic acid group at one end; 150 parts of methylmethacrylate and Synthesis Example 3 were placed in a separable flask equipped with a condenser and a dropping funnel.
0.876 parts of 3-mercaptopropylboronic acid ethylene glycol ester obtained in 1. was charged, and nitrogen substitution was performed. Next, the temperature was raised to 80 ° C., and a separately prepared 0.23% toluene solution of azobisisobutyronitrile was first added to 1.3.
After the addition of 0.4 parts, 0.43 parts was added every 30 minutes. After 5 hours, the mixture was cooled to stop the polymerization. The polymerization rate at this time is 47%
was. The obtained polymethylmethacrylate was reprecipitated with methanol and then dried to obtain polymethylmethacrylate having an average molecular weight of 25,000 and having a boronic acid ethylene glycol ester group at one end of 0.03 meq / g.

Synthesis Example 5 Synthesis of polystyrene having a boronic acid group at one end; 500 parts of styrene and 3-mercaptopropylboronic acid ethylene glycol ester obtained in Synthesis Example 3 were placed in a separable flask equipped with a condenser and a dropping funnel. (MPB
E) 0.0765 part was charged and the atmosphere was replaced with nitrogen. Next, the temperature was raised to 120 ° C., and a styrene solution containing 0.394% MPBE and 0.069% azobiscyclohexanecarbonitrile was initially added in an amount of 6.6 parts, and then 0.45 parts / minute. After 3.5 hours, the mixture was cooled to stop the polymerization. The polymerization rate at this time was 45%. The polystyrene obtained was reprecipitated with methanol and then dried to obtain 0.013 meq of boronic acid ethylene glycol ester group at one end.
A polymethylmethacrylate having an average molecular weight of 68,000 having a weight ratio of / g was obtained.

Example 1 Polyvinyl acetate (hereinafter abbreviated as PVAc) (degree of polymerization 1
700) was poured into methanol, the temperature was raised to 50 ° C. with stirring to dissolve, and the mixture was cooled to room temperature.
A methanol solution having a concentration of 30% was prepared. This solution 20
Polyethylene glycol having a boronic acid group at one end of Synthesis Example 1 in 0 part (hereinafter, polyethylene glycol is PE
6 parts (abbreviated as G) was added, and then 12 parts of 10% NaOH methanol solution was added with stirring at 40 ° C. to saponify to obtain a gel. After crushing this gel with a mixer, it was dried at 100 ° C. for 2 hours to obtain a resin composition. When the saponification degree of the PVA polymer in this resin composition was measured by NMR, it was 98.6 mol%. 100 parts of this resin composition was dissolved in 600 parts of water and cast on a rotary drum having a surface temperature of 75 ° C. to form a film, thereby obtaining a film having a dry thickness of 40 μm. This film is length 3
cm, width 3 cm, embed in diatomaceous earth and let stand in a constant temperature bath at 50 ° C for 30 days, then PEG in the film
The change in content was investigated. Quantitatively determined by NMR, the initial value was 20.3%, which was 19.7% even after 30 days.
There was almost no transfer of G to diatomaceous earth.

Comparative Example 1 Unmodified PE was used instead of PEG having a boronic acid group at one end.
Saponification was performed in the same manner as in Example 1 except that G (average molecular weight 350) was used, and the degree of saponification of the PVA-based polymer was 98.
An 8 mol% resin composition was obtained. A film was prepared from this resin composition, embedded in diatomaceous earth and subjected to a standing test. The PEG content decreased from the initial 20.1% to 4.1%, and most of the PEG was transferred to diatomaceous earth.

Example 2 PVAc modified with 3 mol% sodium 2-acrylamido-2-methylpropanesulfonate in place of polyvinyl acetate
Saponification was performed in the same manner as in Example 1 except that (polymerization degree 1700) was used to obtain a resin composition having a PVA polymer saponification degree of 98.4 mol%. A film was prepared from this resin composition, embedded in diatomaceous earth and subjected to a standing test. The initial value of PEG content is 20.2%, but it remains 1 even after 30 days.
It was 9.9%, and there was almost no transfer of PEG to diatomaceous earth.

Comparative Example 2 Unmodified PE was used instead of PEG having a boronic acid group at one end.
Saponification was performed in the same manner as in Example 2 except that G (average molecular weight 350) was used, and the degree of saponification of the PVA-based polymer was 98.
A 5 mol% resin composition was obtained. A film was prepared from this resin composition, embedded in diatomaceous earth and subjected to a standing test. The PEG content decreased from the initial 20.0% to 3.6%, and most of the PEG was transferred to diatomaceous earth.

Example 3 The ethylene oxide-propylene oxide copolymer obtained in Synthesis Example 2 was used in place of PEG having a boronic acid group at one end, and 3% of a 10% NaOH methanol solution was added.
Saponification was carried out in the same manner as in Example 1 except for the parts
A resin composition in which the saponification degree of the A-based polymer was 73.7 mol% was obtained. A film was prepared from this resin composition, embedded in diatomaceous earth and subjected to a standing test. The initial value of the content of ethylene oxide-propylene oxide copolymer was 19.
Even after 30 days, 9% was 19.6%, and there was almost no transfer to diatomaceous earth.

Comparative Example 3 Example 4 was repeated except that an ethylene oxide-propylene oxide copolymer having an allyl group at one end and an average molecular weight of 1600 was used instead of the ethylene oxide-propylene oxide copolymer having a boronic acid group at one end. Saponification was carried out in the same manner as in Example 3 to obtain a resin composition having a PVA polymer saponification degree of 74.3 mol%. A film was prepared from this resin composition, embedded in diatomaceous earth and subjected to a standing test. The content of ethylene oxide-propylene oxide copolymer decreased from the initial 20.1% to 5.3%.
Most of the G was transferred to diatomaceous earth.

From the results of Examples 1 to 3 and Comparative Example 3 described above, the composition of the present invention is useful as a PVA film material having no plasticizer migration.

Example 4 PVAc modified with allyl acetate 6 mol% (average degree of polymerization: 5)
50 parts of a 30% methanol solution of 50) and 300 parts of a 10% THF solution of polymethylmethacrylate having a boronic acid group at one end of Synthesis Example 4 are mixed, and 12 parts of a 10% NaOH methanol solution are stirred at 40 ° C. Saponification was carried out to obtain a slurry-like mixture. Add this mixture to 10
It dried at 0 degreeC for 2 hours, and obtained the resin composition. When the saponification degree of the PVA polymer in this resin composition was measured by NMR, it was 99.1 mol%. The resin composition 20
Parts and unmodified polymethylmethacrylate (parapet G,
80 parts of Kuraray Co., Ltd. were mixed, melt-kneaded at 220 ° C. for 10 minutes using a Labo Plastomill, and then hot pressed at 230 ° C. to obtain a film having a thickness of 50 μm. The film has good transparency, 20 ° C, 65%
Surface resistivity measured after RH for 1 week was 5.8 x 1
It was 0 ¹¹ Ω / □.

Comparative Example 4 In Synthesis Example 4, 2-mercaptopropylboronic acid ethylene glycol ester was replaced with 0.876 parts to give 2-mercaptopropylboronic acid.
PVA-based polymer was saponified in the same manner as in Example 4 except that polymethylmethacrylate (average molecular weight 25000) having a 2-hydroxyethylthiyl group at one end synthesized using 0.464 part of mercaptoethanol was used. A resin composition having a saponification degree of 98.7 mol% was obtained. When a film was prepared in the same manner as in Example 4, the film had poor transparency and became cloudy.
The surface resistivity measured after humidity control for 1 week was 7.9 × 10 ¹³
It was Ω / □.

Example 5 200 parts of a 30% methanol solution of PVAc (average degree of polymerization 450) modified with 5 mol% of ethyl vinyl ether, and 5 parts of polystyrene of Example 5 having a boronic acid group at one end
% THF solution (600 parts) is mixed and saponified with 10% NaOH methanol solution (12 parts) while stirring at 40 ° C. to produce PV.
A resin composition having a saponification degree of the A-type polymer of 99.0 mol% was obtained. 20 parts of the resin composition and 80 parts of unmodified polystyrene (Styron 666; manufactured by Asahi Chemical Industry Co., Ltd.) are mixed,
After melt-kneading at 190 ° C. for 10 minutes, hot pressing was performed at 210 ° C. to obtain a film having a thickness of 50 μm. The film has good transparency and is 1 at 20 ° C. and 65% RH.
The surface resistivity measured after weekly humidity control is 2.2 × 10 ¹¹ Ω /
It was □.

Comparative Example 5 In Synthesis Example 5, 2-mercaptopropylboronic acid ethylene glycol ester was replaced with 0.475 parts by addition of 2-
Synthesized using 0.254 parts of mercaptoethanol,
A resin composition in which saponification was performed in the same manner as in Example 5 except that polystyrene having a 2-hydroxyethylthiyl group at one end (average molecular weight 65000) was used, and the degree of saponification of the PVA-based polymer was 99.2 mol%. Got When a film was prepared in the same manner as in Example 5, the film had poor transparency and became cloudy, and the surface resistivity measured after humidity conditioning at 20 ° C. × 65% RH for 1 week was 5.8 × 10 ^12. It was Ω / □.

From the results of Examples 4 to 5 and Comparative Examples 4 to 5 described above, it is clear that by using the composition of the present invention, molded articles having good transparency and excellent antistatic properties can be obtained. is there.

[0049]

According to the method for producing a resin composition of the present invention, a resin composition having excellent compatibility and good transparency can be obtained only when the polymer (B) is a saponified hydroxyl group. It is considered that this is because the functional group of the polymer (A) is bonded by the transesterification reaction. The resin composition obtained by the production method of the present invention is excellent in compatibility and transparency and is useful for various applications. An example is shown below. The resin composition of the present invention comprises a polymer (A) and a polymer (B).
Shows a very wide range of physical properties depending on the combination of the above, particularly the properties of the polymer (A), and the following examples are given. First, when the polymer (A) is water-soluble or water-dispersible and has a softening point sufficiently lower than room temperature, it has sufficient flexibility and impact resistance even at low temperature and low humidity, and has a plasticizer added. It is useful for molded articles such as water-soluble films, sheets, bottles, etc., whose physical properties do not change with time. On the other hand, when the softening point is sufficiently higher than room temperature, it is useful as a paper-working material that gives the paper elasticity. Further, when the polymer (A) is water-insoluble and has a softening point sufficiently lower than room temperature, it is useful as a flexible material having water resistance such as a molded product such as a film or sheet or a photosensitive resin material. . On the other hand, when the softening point is sufficiently higher than room temperature, it is useful as a hygroscopic or water-absorbing molded article.

Front page continuation (72) Inventor Toshiaki Sato 1621 Sakata, Kurashiki, Okayama Prefecture Kuraray Co., Ltd. (72) Inventor Hitoshi Maruyama 1621 Sakata, Kurashiki, Okayama Ura

Claims (1)

[Claims] 1. A polymer (A) having at one end a functional group selected from the group consisting of a boronic acid group, a borinic acid group and a boron-containing group which can be converted into a boronic acid group or a borinic acid group in the presence of water. A method for producing a resin composition, comprising saponifying the vinyl ester polymer (B) in the presence of