JPH08217820A - Plasticizer or flexibilizer for polymer and thermoplastic polymer composition - Google Patents

Abstract

PURPOSE: To obtain at a low cost a plasticizer or a softener for polymers, consisting of a specific lactone-modified PVA, free from fuming, bleedout, etc., in molding operations, excellent in compatibility with polymers and suitable for improving the molding processability and softness of polymers. CONSTITUTION: This plasticizer or softener comprises a lactone-modified PVA of the formula (R<1> is a 2-10 C alkylene; R<2> is H or acetyl; n is an average number of mols of added lactone ranging from 1 to 10; X, Y, and Z are each molar composition percentage, being 5 to 90, 0 to 30, and 10 to 95, respectively, and X+Y+Z=100; The constitutive components, the molar compositions of which are represented by X, Y and Z, are randomly bonded). The lactone- modified PVA of the formula is obtained, for example, by melt kneading 5 to 90 pts.wt. of (A) PVA, 10 to 95 pts.wt. of (B) lactone monomer, and 0.001 to 0.1 pts.wt. of a polymerization catalyst, under the conditions that (A+B) totals 100 pts.wt. and the temperature thereof is 50 to 250 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasticizer or a softener added to a thermoplastic and inflexible polymer and a thermoplastic polymer composition, and more specifically, a molded article such as a sheet or a tray, Adhesives, adhesives, ceramics binders, antistatic agents, resin additives such as antifog agents, plasticizers for polar polymers, softeners, surface protection films, packaging films, thickeners, lubricating oils, water-absorbing polymer materials , Hardened material, protective colloid, emulsifying agent, water soluble toilet flushing toilet cleaner, biodegradable and medical applications, and lactone-modified polyvinyl alcohol for improving moldability and toughness of polymer Plasticizer or softener consisting of, and a thermoplastic polymer obtained by mixing the lactone-modified polyvinyl alcohol with a hydrophilic or polar polymer. It relates to a composition.

[0002]

2. Description of the Related Art Polyvinyl alcohol resin films are excellent in aroma retention, transparency, oil resistance, oxygen barrier property, and heat retention property, and are water-soluble, and are suitable for ordinary hydrophobic polymer films. It can also be used for non-use applications. However, polyvinyl alcohol is hard and cannot be molded without using a plasticizer. When a plasticizer is used, there is a problem with smoke generation and bleeding phenomenon during molding. For this reason,
A method of introducing an oxyalkylene group into polyvinyl alcohol for the purpose of softening the polyvinyl alcohol has been proposed. For example, USP 1,971,662, USP
No. 2,844,570 and USP 2,990,398 describe addition reaction of polyvinyl alcohol with ethylene oxide. Also, USP 3,033,841
In JP-A No. 1994-1999, graft polymerization of vinyl acetate with polyethylene glycol and subsequent saponification yields polyvinyl alcohol modified with polyethylene glycol. Also, USP 4,618,648, USP 4,369,
No. 281 describes saponification of a polymer obtained by graft-polymerizing vinyl acetate in the presence of polyalkylene glycol. In addition, USP 4,618,648, USP
No. 4,675,360 shows a copolymer of vinyl alcohol and poly (alkyleneoxy) acrylate. This copolymer can be injection-molded and extruded. It is described as having flexibility and flexibility.

[0001]

However, although these oxyalkylene group-containing polyvinyl alcohols are more flexible than polyvinyl alcohol, they are not flexible at low temperatures, and even at room temperature, depending on the intended use, the flexibility is satisfactory. There were many cases where I could not. Therefore, a plasticizer is added to the above-mentioned polyvinyl alcohol having an oxyalkylene group for the purpose of further improving the molding processability. For example, Japanese Patent Laid-Open No. 3-20
Polyethylene glycol and polypropylene glycol are used as plasticizers in Japanese Patent No. 3932, and nylon 11, nylon 12 and polyester elastomers are used as plasticizers in Japanese Patent Application Laid-Open No. 6-271736. However, in the former case, the drawbacks such as smoke generation and bleed-out at the time of molding cannot be eliminated, and in the latter case, not only the plasticizer is expensive, but also the transparency and rigidity of the molded article are significantly lowered.

Further, a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol is used for an intermediate film of glass or the like because of its advantages such as transparency and rigidity.
Similar to the polyvinyl acetal resin, these are difficult to mold and are usually used by mixing a large amount of ester plasticizers. Therefore, the polyvinyl acetal-based resin may also suffer from defects such as smoke generation and bleed-out during molding, like polyvinyl alcohol. Therefore, an excellent plasticizer that can be used for polyvinyl acetal resins is desired.

In addition, polymers other than the above-mentioned polyvinyl alcohol and polyvinyl acetal resins are also plasticizers or softeners for improving the moldability and flexibility of the polymers, such as smoke and bleed-out during molding. There is a need for new plasticizers or softeners that have a high molecular weight, excellent compatibility with polymers, and are inexpensive.

[0004]

The present inventors have found that by adding a specific amount of lactone to polyvinyl alcohol,
The resulting lactone-modified polyvinyl alcohol has excellent compatibility with various hydrophilic or polar polymers,
They have found that they can be excellent plasticizers or softeners that do not generate smoke or bleed out during molding, and have completed the present invention.

That is, the first aspect of the present invention is to provide a plasticizer or softener for a polymer comprising a lactone-modified polyvinyl alcohol represented by the general formula (1).
Further, a second aspect of the present invention is characterized in that 5 to 80% by weight of the lactone-modified polyvinyl alcohol represented by the general formula (1) and 20 to 95% by weight of a hydrophilic or polar polymer are mixed to form a thermoplastic resin. A polymer composition is provided. Hereinafter, the present invention will be described in detail.

[0004]

Embedded image

In the present invention, the range of X in the general formula (1) is 5 ≦ X ≦ 90, preferably 10 ≦ X ≦ 85,
More preferably, 15 ≦ X ≦ 80. When X is less than 5 mol%, the hydrophilicity of the lactone-modified polyvinyl alcohol is significantly reduced, while when it is more than 90 mol%, the function of the raw material polyvinyl alcohol is almost the same and the hydrophilicity or It is not preferable because the compatibility with the polar polymer and the plasticizing effect are reduced.

The range of Y is 0≤Y≤30, preferably 0≤Y≤20, and more preferably 0≤Y≤15. When Y exceeds 30 mol%, the amount of lactone addition must be reduced in order to maintain hydrophilicity,
It is not preferable because the flexibility and plasticizing effect of the lactone-modified polyvinyl alcohol are reduced. On the contrary, in order to control the balance of functions of hydrophilicity (compatibility with hydrophilic polymer or polar polymer), flexibility and plasticizing effect, Y
Is preferably adjusted to an optimum mol% within the range of 0 ≦ Y ≦ 30.

The range of Z is 10≤Z≤95, preferably 15≤Z≤90, more preferably 20≤Z≤85.
Is. When Z is less than 10 mol%, the function of the raw material polyvinyl alcohol is almost the same, and conversely 9
When it exceeds 5% by weight, the hydrophilicity of the lactone-modified polyvinyl alcohol is significantly reduced, which is not preferable.

R ¹ is an alkylene group having 2 to 10 carbon atoms. Specifically, a pentylene group, a pentylene group substituted with a methyl group, a butylene group, an ethylene group and the like are preferable, and the most industrially useful lactone. R ¹ of the monomer ε-caprolactone corresponds to the pentylene group.

R ² is basically a hydrogen atom or an acetyl group. The molar composition of the hydrogen atom and the acetyl group is not particularly limited and can be set by adjusting the production method, production conditions and the like of the lactone-modified polyvinyl alcohol of the present invention.

N is the average number of lactones added, and 1≤n≤
It is 10, preferably 1.2 ≦ n ≦ 7, and more preferably 1.5 ≦ n ≦ 5. When n is less than 1, the function of the lactone-modified polyvinyl alcohol is the same as that of the raw material polyvinyl alcohol itself,
When it is more than 10, the hydrophilicity of the lactone-modified polyvinyl alcohol is almost lost, and the compatibility with the hydrophilic polymer is significantly reduced, which is not preferable.

The solubility of the lactone-modified polyvinyl alcohol used in the plasticizer or softening agent of the present invention in a solvent greatly changes depending on the amount of lactone modification, and when the amount of lactone modification is small, it is water-soluble and the amount of lactone modification is As the amount increases, it becomes less water-soluble and water-insoluble and becomes soluble in organic solvents such as chloroform and THF.

The degree of polymerization of oxyethylene units in the main chain portion of the lactone-modified polyvinyl alcohol of the present invention is 1
00-10,000, preferably 200-2,000,
More preferably, it is in the range of 300 to 1,000. When the degree of polymerization is less than 100 or more than 10,000, it is difficult to produce polyvinyl alcohol as a raw material, and the lactone cannot be substantially modified.

The melt viscosity of the lactone-modified polyvinyl alcohol used in the present invention can be used as a value showing moldability. Usually measured with a melt flow tester,
Viscosity measured at a load of 10 kg / cm ² using an orifice with a diameter of 1 mm and a length of 1 cm is at least 140 ° C.
10 poise at maximum, 30,000p at 260 ° C
It is about oise. Naturally, the optimum viscosity differs depending on the application, but the load measured at 160-240 ° C is 10 kg / c
Those having a melt viscosity of m ² in the range of 10 to 10,000 poise have good moldability and are easy to handle.

The method for producing the lactone-modified polyvinyl alcohol which is the plasticizer or softener of the present invention will be described in detail. The polyvinyl alcohol used in the present invention is usually obtained by completely or partially saponifying polyvinyl acetate.

The degree of polymerization of the oxyethylene units of the polyvinyl alcohol is in the range of 100 to 10,000, preferably 200 to 2,000, and more preferably 300 to 1,000. Degree of polymerization is 100
Those of less than 10,000 and more than 10,000 are not preferable because they are difficult to manufacture. The degree of polymerization is selected so that the lactone-modified polyvinyl alcohol used in the present invention has an appropriate melt viscosity, and the degree of polymerization of polyvinyl alcohol is 200 to 2,000.
0 is easy to handle.

The saponification degree of the polyvinyl alcohol is usually 70 mol% or more, preferably 8
It is 0 mol% or more, more preferably 85 mol% or more.
If the degree of saponification is less than 70 mol%, the amount of lactone added must be reduced in order to maintain the hydrophilicity of the lactone-modified polyvinyl alcohol, and the flexibility and plasticizing effect are reduced, which is not preferable. . On the contrary, to control the balance of functions of hydrophilicity, flexibility and plasticizing effect,
It is preferable to adjust to an optimum mol% of 70 mol% or more.

Specific examples of the lactone monomer used in the present invention include methylated caprolactone such as ε-caprolactone and 4-methylcaprolactone, δ-valerolactone and β-propiolactone. Industrially most useful ε-caprolactone is preferably used.

The polymerization catalyst used in the present invention is
It is a ring-opening addition polymerization catalyst of a lactone monomer. Specifically, inorganic bases, inorganic acids, organic alkali metals, tin compounds, titanium compounds, aluminum compounds, zinc compounds,
Examples thereof include molybdenum compounds and zirconium compounds. Among them, tin compounds, titanium compounds and aluminum compounds are preferably used in terms of balance of ease of handling, low toxicity, reactivity, non-coloring property, thermal stability and the like.
Specifically, stannous chloride, stannous octylate, monobutyltin oxide, monobutyltin compounds such as monobutyltin tris (2-ethylhexanate), dibutyltin compounds such as dibutyltin oxide, tetrabutyl titanate, tetra-iso. -Propyl titanate, alkyl-di (phenoxy) -aluminum and the like. These may be used alone or as a mixture.

The method for producing the lactone-modified polyvinyl alcohol used in the present invention is as follows.
0 parts by weight, 10 to 95 parts by weight of lactone monomer (total of 100 parts by weight of both) and polymerization catalyst 0.001 to 0.1
It can be obtained by melt-kneading parts by weight at a temperature of 50 to 250 ° C. If the polyvinyl alcohol content is less than 5 parts by weight and the lactone monomer content exceeds 95 parts by weight, the hydrophilicity of the resulting lactone-modified polyvinyl alcohol is significantly reduced, which is not preferable. On the other hand, when the amount of polyvinyl alcohol exceeds 90 parts by weight and the lactone monomer is less than 10 parts by weight, the function of the raw material polyvinyl alcohol is not changed, which is not preferable. The mixing ratio of the polyvinyl alcohol, which is a raw material of the lactone-modified polyvinyl alcohol, and the lactone monomer in the present invention is optimal depending on the compatibility of the polymer to be mixed with the obtained lactone-modified polyvinyl alcohol, the flexibility, and the functional balance of the plasticizing effect. It is preferable to carry out at a mixing ratio.

The amount of polymerization catalyst added is 100 in total for both raw materials.
The range of usually 0.001 to 0.1 parts by weight with respect to parts by weight,
Preferably 0.002-0.05 parts by weight, especially 0.0
It is in the range of 05 to 0.01 parts by weight. When the amount of the catalyst is 0.
When it is less than 001 parts by weight, the addition polymerization rate of the lactone monomer is slow, and when it is more than 0.1 parts by weight,
The lactone-modified polyvinyl alcohol obtained is not preferable because it may be colored or its thermal stability may be deteriorated.

The polymerization temperature is usually in the range of 50 to 250 ° C., preferably 100 to 220 ° C., more preferably 160 to 200 ° C. When the temperature is lower than 50 ° C, the addition polymerization rate of the lactone monomer is slow, while when it is higher than 250 ° C, the thermal decomposition reaction of polyvinyl alcohol occurs, and coloring or a decomposition product is generated, which is not preferable. .

Regarding the production apparatus for carrying out the melt kneading in the method for producing the lactone-modified polyvinyl alcohol used in the present invention, a known melt kneading machine can be used without any problem. Specifically, a stirring blade type batch kneader, a kneader type kneader, a screw type kneader such as an extruder, a static mixer type kneader, and the continuous connection of these devices can be used. Further, in the above-mentioned production method, the order of addition of the raw materials, the polymerization catalyst and the additive, and the addition method are not limited at all.

Further, the amount of water contained in the raw material is 1.0
It is desirable that the content be less than or equal to wt%, preferably less than or equal to 0.5% by weight, and more preferably less than or equal to 0.1% by weight. If the amount of water contained in the raw material exceeds 1.0% by weight, the addition polymerization of the lactone monomer from the water may occur to form a polylactone oligomer, which is not preferable.

The hydrophilic or polar polymers used in the present invention are both thermoplastic and exhibit good compatibility with the lactone-modified polyvinyl alcohol. For example,
A general hydrophilic polymer has good compatibility with a lactone-modified polyvinyl alcohol having a small amount of lactone modification.

The above-mentioned hydrophilic polymers include completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, completely or partially saponified ethylene-vinyl acetate copolymer, polyethylene glycol, polypropylene glycol, polyvinyl ether, acetal. Examples thereof include polysaccharides such as polyvinyl acetal, polyglycerin, polyepichlorohydrin, starch and cellulose having a low degree of conversion, polypeptides, and polyamino acids.

As the lactone-modified polyvinyl alcohol having a small amount of lactone modification, the weight ratio of the polyvinyl alcohol component to the entire lactone-modified polyvinyl alcohol is 40% by weight or more, preferably 50% by weight, more preferably 60% by weight or more. Of (90
Wt% or less). Of the above-mentioned hydrophilic polymers, completely or partially saponified polyvinyl alcohol is highly important to be plasticized, and has very good compatibility with lactone-modified polyvinyl alcohol having a small amount of lactone modification, and therefore has a value in application. Is high.

The polar polymer in the present invention has good compatibility with lactone-modified polyvinyl alcohol having a large amount of lactone modification. As such a polar polymer,
Examples include polyvinyl acetal, polyoxymethylene, polyoxymethylene copolymer, polyamide, polyester, polycarbonate, polymethylmethacrylate, poly (styrene-acrylonitrile) copolymer, polyimide, polysulfone, polyethersulfone, polyetheretherketone. .

As the lactone-modified polyvinyl alcohol having a large amount of lactone modification, the weight ratio of the polyvinyl alcohol component to the whole lactone-modified polyvinyl alcohol is 50% by weight or less, preferably 40% by weight, more preferably 30% by weight. The following (5% by weight or more). Among the polar polymers, polyvinyl acetal, polyoxymethylene and polyoxymethylene copolymers are highly important to be plasticized, and
It has a very good compatibility with lactone-modified polyvinyl alcohol, which has a large amount of lactone-modified amount, and thus has high application value.

The thermoplastic resin composition according to the second aspect of the present invention is a mixture of 5 to 80% by weight of the lactone-modified polyvinyl alcohol represented by the general formula (1) and 20 to 95% by weight of a hydrophilic or polar polymer. However, the proportion of the former in the whole is preferably 10 to 70% by weight, more preferably 15 to 75% by weight. When the ratio of the former in the whole is less than 5% by weight, the plasticizing effect and the degree of flexibility cannot be satisfied, and when it exceeds 80% by weight, it becomes too flexible and the hydrophilic or polar polymer is originally This is not preferable because the rigidity of is lost.

In the second aspect of the present invention, the method of mixing the lactone-modified polyvinyl alcohol and the hydrophilic or polar polymer is not particularly limited, but a method of mixing using a known melt kneader is preferable. As the above kneader, a stirring blade type batch kneader, a kneader type kneader,
Examples thereof include a screw type kneader such as an extruder, a static mixer type kneader, and continuous use of these devices. The kneading temperature is usually 100 to 2
The temperature is in the range of 80 ° C, preferably 140 to 240 ° C, more preferably 160 to 200 ° C. When the temperature is lower than 100 ° C, it becomes difficult to uniformly mix the former with 280
If the temperature is higher than 0 ° C., a thermal decomposition reaction of polyvinyl alcohol occurs, and coloring or a decomposed product is generated, which is not preferable.

In the method of mixing the lactone-modified polyvinyl alcohol represented by the general formula (1) with the hydrophilic or polar polymer, the polyvinyl alcohol and the lactone monomer constituting the lactone-modified polyvinyl alcohol together with the polymerization catalyst are directly hydrophilic. A method of melt-kneading with a hydrophilic or polar polymer and advancing the lactone polyaddition of the lactone-modified polyvinyl alcohol while simultaneously mixing with a hydrophilic or polar polymer can also be preferably adopted.

Further, for the lactone-modified polyvinyl alcohol which is the plasticizer or softener for the polymer according to the first aspect of the present invention, or for the thermoplastic resin composition according to the second aspect of the present invention, an antioxidant, There is no particular limitation on the mixture use of heat stabilizers, known additives such as plasticizers other than lactone-modified polyvinyl alcohol, other thermoplastic resins, and inorganic fillers unless the effects of the present invention are impaired.

[0033]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.

(Measurement of Melt Viscosity) The melt viscosity in this example is measured by using a capillary rheometer.
Orifice 1mm × 1cm, temperature 240 ℃, load 100
It was measured under the condition of kg / cm ² .

(Production Example 1) In a 1-liter glass flask, polyvinyl alcohol PVA-1 manufactured by Kuraray Co., Ltd.
17 (Saponification degree 98.0 ± 0.5, Polymerization degree 1,700)
300 g, 700 g of ε-caprolactone and 0.02 g of stannous chloride as a polymerization catalyst were added, the temperature was raised to 180 ° C., and melt kneading was performed for 5 hours. The values of X, Y, Z and n in the general formula (1) of this product are 5 respectively.
It was 5, 0, 45 and 2.0. The obtained polymer is referred to as lactone-modified polyvinyl alcohol (1).

(Production Example 2) Polyvinyl alcohol PVA-2 manufactured by Kuraray Co., Ltd. was placed in a 1-liter glass flask.
03 (Saponification degree 88.0 ± 1.0, Polymerization degree 300) 40
0 g, 400 g of ε-caprolactone and 0.02 g of stannous chloride as a polymerization catalyst were added, the temperature was raised to 180 ° C., and melt kneading was performed for 5 hours. General formula (1) of this thing
The values of X, Y, Z and n in are 66 and 1, respectively.
It was 2, 22 and 1.8. The obtained polymer is
The lactone-modified polyvinyl alcohol (2) is used.

(Production Example 3) Polyvinyl alcohol PVA-4 manufactured by Kuraray Co., Ltd. was placed in a 1-liter glass flask.
03 (saponification degree 81.5 ± 1.5, polymerization degree 300) 10
0 g, ε-caprolactone 900 g, and polymerization catalyst monobutyltin tris (2-ethylhexanate) 0.0
5 g was added, the temperature was raised to 160 ° C., and melt kneading was performed for 3 hours. X, Y in the general formula (1) of this product,
The values of Z and n were 14, 20, 66 and 6.2, respectively. The obtained polymer is designated as lactone-modified polyvinyl alcohol (3).

(Examples 1 to 3) Polyvinyl acetal "S-REC BX-3Z" manufactured by Sekisui Chemical Co., Ltd. and the lactone-modified polyvinyl alcohol (1) obtained in Production Example 1 were added at the ratios shown in Table 1. Melt-kneading was performed at 180 ° C. for 5 minutes using a Labo Plastomill mixer manufactured by Toyo Seiki Co., Ltd. All the resin compositions obtained were transparent. The melt viscosity of each of these resin compositions was measured using a capillary rheometer, and the results are shown in Table 1.

(Examples 4 and 5) At the ratios shown in Table 2,
Polyoxymethylene copolymer DURACON M90-01 manufactured by Polyplastics Co., Ltd. and the lactone-modified polyvinyl alcohol (1) obtained in Production Example 1 were used at 180 ° C. using a Labo Plastomill mixer manufactured by Toyo Seiki Co., Ltd. Melt kneading was performed for 5 minutes. The melt viscosity of the obtained resin composition was measured in the same manner as in Example 1, and the results are shown in Table-2.

(Examples 6 and 7) At the ratios shown in Table 3,
Kuraray Co., Ltd. polyvinyl alcohol PVA-117
The lactone-modified polyvinyl alcohol (2) obtained in Production Example 2 was melt-kneaded at 180 ° C. for 5 minutes using a Labo Plastomill mixer manufactured by Toyo Seiki Co., Ltd. All of these resin compositions were transparent. Further, the melt viscosity of the obtained resin composition was measured, and the results are also shown in Table 3.

(Example 8) 30 g of polyvinyl acetal "S-REC BX-3Z" manufactured by Sekisui Chemical Co., Ltd. and polyvinyl alcohol "PVA-103" manufactured by Kuraray Co., Ltd. in a Labo Plastomill mixer manufactured by Toyo Seiki Co., Ltd. 2
g, and 18 g of caprolactone monomer were charged, 1
It is heated to 80 ° C and monobutyltin tris (2
-Ethyl hexanate) 0.02 g was added, and the temperature was 180 ° C.
Melt kneading was performed for 10 minutes to obtain a transparent resin composition. The melt viscosity of this resin composition was measured using a capillary rheometer. The results are shown in Table-4.

(Examples 9 to 11) The polyvinyl acetal "S-REC BX-3Z" manufactured by Sekisui Chemical Co., Ltd. and the lactone-modified polyvinyl alcohol (3) obtained in Production Example 3 were mixed in the proportions shown in Table 4. Melt-kneading was performed at 180 ° C. for 5 minutes using a Labo Plastomill mixer manufactured by Toyo Seiki Co., Ltd. All the resin compositions obtained were transparent. In addition, the melt viscosity of these resin compositions was measured using a capillary rheometer. The results are shown in Table-4.

Comparative Examples 1 to 3 Examples 1 to 3 for comparison
The melt viscosities of the polyvinyl acetal, polyoxymethylene copolymer and polyvinyl alcohol used in 1. were measured using a capillary rheometer. Table of results
It is described together with 1-3.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

According to the plasticizer comprising the lactone-modified polyvinyl alcohol represented by the general formula (1) of the present invention,
Moldability of these resin compositions can be increased by adding them to hydrophilic polymers such as polyvinyl acetal and polar polymers such as polyoxymethylene copolymers. At that time, the compatibility between each resin and the plasticizer or softener according to the present invention is also extremely excellent.

Claims (2)

[Claims] 1. A plasticizer or softener for a polymer comprising a lactone-modified polyvinyl alcohol represented by the general formula (1). Embedded image 2. A thermoplastic polymer composition comprising 5 to 80% by weight of the lactone-modified polyvinyl alcohol represented by the general formula (1) and 20 to 95% by weight of a hydrophilic or polar polymer.