JP2021020988A - Vinyl chloride-based polymer composition, method for producing the same and use thereof - Google Patents

Abstract

To provide: a vinyl chloride-based polymer composition capable of obtaining a molded product which maintains flame-retardancy or high heat-insulating property specific to a vinyl chloride-based polymer composition and has excellent elastic modulus and heat resistance; a method for producing the same; and an application represented by a window frame.SOLUTION: There is provided a vinyl chloride-based polymer composition which comprises (A) a chemically modified cellulose nanofiber and (B) a vinyl chloride-based polymer and optionally (C) an ethylene-vinyl acetate-based copolymer, wherein the chemically modified cellulose nanofiber (A) has a crystallinity of 42.7% or more and 90.0% or less, the substitution degree by an acyl group of a hydroxyl group of a sugar chain constituting a cellulose nanofiber is 0.56 or more and 2.52 or less and the cellulose of the cellulose nanofiber uses a chemically modified cellulose nanofiber which is lignocellulose.SELECTED DRAWING: None

Description

The present invention relates to a vinyl chloride-based polymer composition, a method for producing the same, and its use. Specifically, the present invention is a molding having excellent elastic modulus, heat resistance, and environmental properties while maintaining flame retardancy and high heat insulating properties. The present invention relates to a vinyl chloride-based polymer composition from which a product can be obtained, a method for producing the same, and uses represented by a window frame.

Vinyl chloride-based polymers and their compositions have been excellent in rigidity, weather resistance, flame retardancy, etc., and have been used for pipes, window frames, flat plates, etc. by extrusion molding because of their low cost and high productivity. , Widely used in fields such as sheets.

Among these, in applications such as window frames, while being excellent in terms of high heat insulation performance and dew-proof performance, the rigidity is about 2000 to 3000 MPa, so that the frame material is required to obtain the wind pressure resistance required for the window frame. Material costs are high due to designing a large wall thickness and outer dimensions, inserting metal reinforcements inside the frame material, etc., so while there are advantages in use such as heat insulation performance, it meets market demands in terms of economy. It is a difficult product.

Further, since the upper limit temperature of the heat resistance of the vinyl chloride resin is about 70 to 90 ° C., when it is used as an exterior member, it may be deformed due to solar heat. In particular, the exterior member of the window frame is easily deformed because it is easily irradiated with sunlight.

The present invention provides a vinyl chloride polymer composition and a method for producing the same, which can obtain a molded product having excellent elastic modulus and heat resistance while maintaining the flame retardancy and high heat insulating properties peculiar to the vinyl chloride polymer. With the goal.

The present invention that solves the above problems is specified by the following matters.
<1> A vinyl chloride-based polymer composition containing (A) chemically modified cellulose nanofibers and (B) vinyl chloride-based polymer, wherein the (A) chemically modified cellulose nanofibers are described below (a). A vinyl chloride polymer composition that satisfies all of the conditions (c) to (c).
(A) The crystallinity of the chemically modified cellulose nanofibers (A) is 42.7% or more and 90.0% or less.
(B) The chemically modified cellulose nanofiber (A) has a hydrogen atom of a hydroxyl group of a sugar chain constituting the cellulose nanofiber in a general formula: (R-CO-, where R is an alkyl group having 1 to 4 carbon atoms. Alternatively, it is substituted with an acyl group represented by (indicating a phenyl group which may have an electron-donating substituent), and the degree of substitution is 0.56 or more and 2.52 or less.
(C) The cellulose of the chemically modified cellulose nanofibers and cellulose nanofibers (A) is lignocellulose.

<2> The above-mentioned <1>, which further contains (C) an ethylene-vinyl acetate-based copolymer, and the (C) ethylene-vinyl acetate-based copolymer satisfies the following conditions (d) and (e). Vinyl chloride-based polymer composition.
(D) The content of vinyl acetate constituting the (C) ethylene-vinyl acetate-based copolymer is 3% by mass or more and 85% by mass or less.
(E) The acetyl group of vinyl acetate constituting the ethylene-vinyl acetate-based copolymer (C) is replaced with a hydrogen atom by a saponification reaction, and the degree of saponification is 0% or more and 95% or less.

<3> All or part of the (B) vinyl chloride-based polymer is a vinyl chloride-based copolymer obtained by graft-polymerizing vinyl chloride on the (D) ethylene-vinyl acetate-based polymer, and the above-mentioned (D). The vinyl chloride-based polymer composition according to <1> or <2>, wherein the vinyl chloride-based copolymer satisfies the following condition (f).
(F) The ethylene-vinyl acetate-based copolymer constituting the vinyl chloride-based copolymer (D) is an ethylene-vinyl acetate-based copolymer satisfying the above conditions (d) and (e), and the content thereof is 0. .3% by mass or more and 40% by mass or less.

<4> All or part of the (B) vinyl chloride-based polymer is a vinyl chloride-based copolymer obtained by copolymerizing (E) vinyl chloride and vinyl acetate, and the (E) vinyl chloride-based copolymer is the same. The vinyl chloride-based polymer composition according to <1> or <2>, wherein the coalescence satisfies the following condition (g).
(G) The content of vinyl acetate constituting the vinyl chloride-based copolymer (E) is 0.3% by mass or more and 30% by mass or less.

<5> The method for producing a vinyl chloride-based polymer composition according to the above <1> to <4>, which comprises the following steps (1) to (3). Method for producing (1) Chemically modified pulp and (B) vinyl chloride polymer, which are (A) chemically modified cellulose nanofibers that satisfy the following conditions (a) to (c) after defibration treatment, are required. (C) Step of selecting ethylene-vinyl acetate-based copolymer according to
(A) The crystallinity of the chemically modified cellulose nanofibers is 42.7% or more and 90.0% or less.
(B) In the chemically modified cellulose nanofiber, the hydrogen atom of the hydroxyl group of the sugar chain constituting the cellulose nanofiber is substituted with an acyl group, and the degree of substitution is 0.56 or more and 2.52 or less.
(C) The cellulose of the chemically modified cellulose nanofibers and cellulose nanofibers is lignocellulose.
(2) Step of blending (A1) chemically modified pulp selected in the step (1), (B) vinyl chloride polymer, and (C) ethylene vinyl acetate copolymer if necessary (3) The (A1) chemically modified pulp, (B) vinyl chloride polymer, and (C) ethylene vinyl acetate copolymer blended in the step (2) are kneaded, and at the same time, (A1) chemically modified pulp is kneaded. A step of defibrating to obtain a vinyl chloride-based polymer composition containing (A) chemically modified cellulose nanofibers, (B) vinyl chloride-based polymer, and, if necessary, (C) ethylene-vinyl acetate-based copolymer.

<6> The step (3) described above is (F) the following general formula (I).
R1-CO-N (R2) -R3 (I) (In the formula, R1 and R3 represent the same or different hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, or R1 and R3 are combined. Indicates an alkylene group having 3 to 11 carbon atoms. R2 mainly represents an amide compound represented by a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 2 to 4 carbon atoms. The method for producing a vinyl chloride-based polymer composition according to <5>, which comprises (A1) a step of accelerating the defibration of a chemically modified pulp by using a defibration aid as an ingredient.

<7> A window frame material comprising the vinyl chloride-based polymer composition according to the above <1> to <4>.

According to the present invention, a vinyl chloride polymer composition and a method for producing the same can be obtained by obtaining a molded product having excellent elastic modulus and heat resistance while maintaining the flame retardancy and high heat insulating properties peculiar to the vinyl chloride polymer. Can be provided.

It is a schematic diagram explaining the manufacturing method of Example 1. 6 is a polarizing microscope observation image of fibers in a sample prepared from the composition produced by the method of Example 1. It is a schematic diagram explaining the manufacturing method of Example 2. 6 is a polarizing microscope observation image of fibers in a sample prepared from the composition produced by the method of Example 2. It is a schematic diagram explaining the manufacturing method of Example 3. 6 is a polarizing microscope observation image of fibers in a sample prepared from the composition produced by the method of Example 3. It is a schematic diagram explaining the manufacturing method of Example 4. 6 is a polarizing microscope observation image of fibers in a sample prepared from the composition produced by the method of Example 4. It is a schematic diagram explaining the manufacturing method of Example 5. 6 is a polarizing microscope observation image of fibers in a sample prepared from the composition produced by the method of Example 5. It is a schematic diagram explaining the manufacturing method of Example 6. 6 is a polarizing microscope observation image of fibers in a sample prepared from the composition produced by the method of Example 6. It is a schematic diagram explaining the manufacturing method of Example 7. 6 is a polarizing microscope observation image of fibers in a sample prepared from the composition produced by the method of Example 7. It is a schematic diagram explaining the manufacturing method of Comparative Example 1. It is a schematic diagram explaining the manufacturing method of the comparative example 2.

1. 1. Explanation of terms and abbreviations The following terms used in the present specification have the following meanings, respectively.

Cellulose-based fibers mean fibers containing cellulosic and / or lignocellulose derived from plants, microorganisms, algae or tunicates (ascidians).

Lignocellulose is a complex hydrocarbon polymer (natural polymer mixture) that constitutes a tree cell wall, and is known to be mainly composed of polysaccharide cellulose, hemicellulose, and lignin, which is an aromatic polymer. .. In the present invention, lignocellulose means a substance composed of cellulose, hemicellulose and lignin regardless of the amount of lignin content and regardless of the presence or absence of chemical bonds between cellulose, hemicellulose and / or lignin. ..

Pulp is a cellulosic fiber derived from a plant separated from the whole plant or a part of the plant such as wood, bamboo, rice straw, and cotton, and is a fiber aggregate containing cellulose, hemicellulose, and / or lignocellulose (plant-derived). Means pulp). In addition, cellulose fiber aggregates derived from microorganisms (pulp derived from microorganisms) separated from a mixture of cellulose produced by microorganisms and bacterial cells derived from microorganisms, cellulose fiber aggregates separated from ascidians (pulp derived from algae), and tail cords Animal Subphylum Animal (Ascidian) means an aggregate of cellulose fibers (pulp derived from ascidian) separated from ascidians.
Ligno pulp means pulp containing lignocellulose.

Chemically modified cellulose nanofibers are synonymous with chemically modified microfibrillated cellulose fibers, and chemically modified microfibrillated cellulose fibers (chemically modified MFCs) mean chemically modified and microfibrillated cellulose fibers. To do. Here, "chemical modification" means that a substituent (chemical modification group) is introduced (the hydroxyl group is chemically modified) instead of the hydrogen atom of the hydroxyl group of the sugar chain constituting the cellulose-based fiber. ..

In the present specification, microfibrillation does not mean that the diameters of the respective fibers are all nano-order, but the diameters of the fibers are nano-order, or the fibers existing inside or on the surface of the fibers are nano-order. It means to be an order. Therefore, even if the diameter of the fiber is nano-order defibrated, and the diameter of the thickest part of the fiber is nano-order or more (for example, several μm to several tens of μm), the surface is defibrated to nano-order. Fibers and fibers in which these fibers are mixed are also interpreted as microfibrillated fibers.

Hereinafter, the vinyl chloride-based polymer composition of the present invention will be described in detail.
The vinyl chloride-based polymer composition of the present invention comprises (A) chemically modified cellulose nanofibers (hereinafter, also referred to as "Chemically Modified MFC") and (B) vinyl chloride-based polymer, if necessary. (C) It contains an ethylene-vinyl acetate-based copolymer, and the chemically modified MFC satisfies all of the following conditions (a) to (c).
(A) The crystallinity of the chemically modified cellulose nanofibers is 42.7% or more and 90.0% or less.
(B) In the chemically modified cellulose nanofiber, the hydrogen atom of the hydroxyl group of the sugar chain constituting the cellulose nanofiber is substituted with an acetyl group, and the degree of substitution is 0.56 or more and 2.52 or less.
(C) The cellulose of the chemically modified cellulose nanofibers and cellulose nanofibers is lignocellulose.

2. 2. (A) Chemically Modified Cellular Nanofiber The chemically modified pulp (hereinafter referred to as "the present defibrating raw material"), which is a raw material for defibrating the chemically modified MFC, will be described.

The defibration raw material is a hydrophobic cellulose-based fiber aggregate in which the hydrogen atom of a part of the hydroxyl group of the cellulosic fiber is replaced with an acyl group (R-CO-).

For the preparation of the defibration raw material, a cellulosic fiber aggregate derived from a plant, a microorganism, an algae, or a tunicate subphylum (Ascidian) can be used. Of these, plant-derived cellulosic fiber aggregates are preferable because they are available in large quantities and are easily available.

Examples of raw materials for plant-derived cellulosic fiber aggregates include wood, bamboo, hemp, jute, kenaf, cotton, beet, agricultural waste, used paper, and knitted fabric. Among these, a cellulosic fiber aggregate derived from wood (also referred to as wood pulp) is preferable because it is easily available.

Wood pulp includes those that do not contain lignin and those that contain lignin (that is, lignocellulosic fiber aggregates, or ligno pulp). All of these can be used for the production of the defibration raw material. Ligno pulp is preferable from the viewpoint of manufacturing cost.

Examples of wood used as a raw material for wood pulp include wood derived from coniferous trees such as sitka spruce, pine (todomatsu, red pine, etc.), sugi, cypress, and broad-leaved trees such as eucalyptus and acacia. The plant-derived pulp obtained from these is preferably used in the production of the defibration raw material.

Wood pulp can be obtained by treating a vegetable raw material by a method such as a mechanical pulping method, a chemical pulping method, or a combination of a mechanical pulping method and a chemical pulping method. Examples of such pulp include kraft pulp and mechanical pulp (MP). Examples of kraft pulp include softwood unbleached kraft pulp (NUKP), softwood oxygen-exposed unbleached kraft pulp (NOKP), softwood bleached kraft pulp (NBKP) and the like. Examples of mechanical pulp include crushed wood pulp (GP), refiner GP (RGP), thermomechanical pulp (TMP), and chemithermomechanical pulp (CTMP). Further, as the pulp, it is also possible to use deinked waste paper, corrugated cardboard waste paper, magazines, copy paper and the like. One type of pulp may be used alone, or two or more types may be mixed and used.

Wood pulp contains lignocellulose and is mainly composed of cellulose, hemicellulose, and lignin. In the present specification, pulp in which lignin is not completely removed and lignin is present in the pulp even in a small amount is referred to as ligno pulp. Therefore, it is obtained by treating with the above-mentioned various pulping methods, and even a small amount can be detected in the pulp. Those containing possible lignin are contained in ligno pulp.

The ligno pulp can be advantageously used in the present invention because the yield from the raw material is large, the number of steps is small, and the amount of processing agent is small. The amount of lignin contained can be quantified by the Clarson method.

In the present invention, wood pulp is subjected to treatments such as decoupling, beating, and defibration using a refiner or a heater or a combination thereof in advance, and the treated Canadian standard freeness (CSF) value (water drainage degree) is obtained. Usually 40 mL to 500 mL, preferably 40 mL to 300 mL, and more preferably 40 mL to 200 mL can be used.

The cellulosic fiber derived from a microorganism can be obtained from, for example, pulp derived from a microorganism obtained by removing proteins and other impurities from a mixture of cellulosic fibers and cells recovered from a culture solution in which acetic acid bacteria are cultured. ..

Microorganism-derived cellulosic fibers are usually entangled with nano-level cellulosic fibers in a mesh pattern, and this can be used as a raw material for hydrophobic cellulose fiber aggregates.

The defibration raw material is characterized in that the hydrogen atom of a part of the hydroxyl group of the cellulosic fiber is substituted with the acyl group.

By selecting an acyl group as a substituent for the hydrogen atom of a part of the hydroxyl group of the defibrating raw material, the defibrating raw material chemically modified with such a substituent has improved thermal stability.

It is considered that this is because in the defibration raw material, the hydrogen bonds between the hydroxyl groups originally existing on the surface of the cellulosic fiber are partially lost, so that they are easily microfibrillated during the defibration treatment.

Since the chemically modified MFC is also hydrophobized by being chemically modified with an acyl group, it has a higher affinity with the vinyl chloride resin because it is more hydrophobic than the original cellulosic fiber, and is contained in the resin. It becomes easy to be evenly dispersed. Therefore, the molded product made of the composition of the present invention containing the chemically modified MFC and the vinyl chloride polymer produced by using the defibration raw material has excellent strength characteristics.

As described above, the defibrating raw material is substituted with an acyl group. The cellulosic fiber chemically modified with an acyl group and microfibrillated, that is, the chemically modified MFC produced by defibrating the defibration raw material has a high affinity with the vinyl chloride polymer composition. It can be uniformly dispersed in the vinyl chloride polymer composition.

In the defibration raw material, the heat resistance of the defibration raw material can be improved by selecting an acyl group as the substituent.

In addition, when preparing the defibration raw material modified with an acyl group, not only can the high crystallinity of cellulose in the pulp of the raw material be maintained, but this high crystallinity is the above-mentioned defibration raw material. The chemically modified MFC produced by defibrating the above can also maintain a high crystallinity (requirement (a)) of 42.7% or more and 90.0% or less. The crystallinity can be analyzed by various analysis methods such as wide-angle X-ray diffraction.

In the acyl group represented by the general formula: (R-CO-), R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may have an electron-donating substituent.

The alkyl group having 1 to 4 carbon atoms includes a linear alkyl group and a branched chain alkyl group. Examples of these linear alkyl groups include methyl, ethyl, n-propyl, and n-butyl, and examples of the branched chain alkyl group include isopropyl and tert-butyl.

As the acyl group in which R is an alkyl group having 1 to 4 carbon atoms, an acyl group having 2 to 5 carbon atoms is preferable. Specific examples of such an acyl group include an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group and a pivaloyl group. These are preferable in that the acylating agent used for acylation is available at a lower cost than other acylating agents. Of these, the acetyl group is more preferable.

Examples of the phenyl group that may have the electron-donating substituent include phenyl, tolyl, ethylphenyl, methoxyphenyl, and ethoxyphenyl.

Specific examples of the acyl group, which is a phenyl group in which R may have an electron-donating substituent, include benzoyl, 4-methylbenzoyl, 4-ethylbenzoyl, 4-methoxybenzoyl, 4-ethoxybenzoyl and the like. .. Among these aromatic acyl groups, benzoyl group, 4-methoxybenzoyl group, and 4-methylbenzoyl group are preferably modified with these groups because cellulose-based fibers having particularly good thermal stability can be obtained. A benzoyl group is more preferable because it is an acylating agent that can be obtained at a lower cost than an aromatic acylating agent and can be introduced into a cellulose-based fiber.

The degree of modification by the acyl group (degree of substitution, also referred to as "DS") in the defibration raw material is that the hydrogen atom of the hydroxyl group existing in one unit (repeating unit) of the cellulosic polymer constituting the cellulosic fiber aggregate. , Represented by the degree of substitution with the substituent.

When the cellulose fiber aggregate is entirely composed of cellulose (in the case of cellulose), this repeating unit is a glucopyranose residue, and the number of hydroxyl groups per unit is 3, so the upper limit of the degree of substitution is 3. Is.

On the other hand, when the cellulosic polymer is lignocellulose, lignocellulose contains hemicellulose and lignin together with cellulose. The number of hydroxyl groups of the xylose residue in xylan and the galactose residue in arabinogalactan contained in hemicellulose is 2, and the number of hydroxyl groups of the standard lignin residue is also 2. Smaller.

Therefore, the upper limit of the degree of substitution in the lignocellulosic fiber aggregate (lignopulp) is less than 3. The upper limit of the degree of substitution depends on the content of hemicellulose and lignin contained in the lignocellulose fiber (lignopulp), and is about 2.7 to 2.8.

As described above, the degree of substitution in the defibration raw material depends on the content of hemicellulose or lignin in the cellulosic fiber assembly, but in the chemically modified MFC obtained by defibrating the defibration raw material as well. The degree of substitution (DS) with the acyl group is 0.56 or more and 2.52 or less (requirement of (b) above), and is preferably 0.6 or more and 1.5 or less. The degree of substitution (DS) is more preferably 0.65 or more and 1.2 or less, and further preferably 0.7 or more and 1.2 or less. In particular, the degree of substitution (DS) when the acyl group is an acetyl group is more preferably 0.8 or more and 1.2 or less. A chemically modified MFC having a DS in the above range is uniformly dispersed in a matrix (vinyl chloride polymer composition) and has a crystallinity in the range of (a). Therefore, such a chemically modified MFC The melt-kneaded composition containing the above has excellent physical properties.

The degree of substitution (DS) can be analyzed by various analytical methods such as neutralization titration, FTIR, and two-dimensional NMR (1H and 13CNMR).

3. 3. Method for producing the defibrated raw material The method for producing the defibrated raw material will be described below.

The defibration raw material can be produced by acylating a part of the hydroxyl groups of the cellulosic fiber with the acyl group represented by the general formula.

As a raw material for this acylation, a plant-derived cellulosic fiber aggregate (pulp) is used.

The pulp is treated with a refiner or heater or a combination thereof in advance to dissociate, beat, defibrate, etc., and the treated Canadian standard freeness (CSF) value (water drainage degree) is 40 mL to 500 mL. Pulp of 40 mL to 300 mL, more preferably 40 mL to 200 mL is used. By using CSF pulp of this degree, it becomes easy to make microfibrils in the defibration treatment step.

As a raw material for producing the defibration raw material, it is preferable to use a wood-derived lignocellulosic fiber aggregate, and in this case, it is more preferable to use ligno pulp. Since ligno pulp is lower in cost than pulp containing no lignin, it is possible to produce a resin composite containing fibers in which the defibrating raw material is fibrillated and a molded product of the present invention, which comprises the same. it can. In order to obtain a melt-kneaded composition with less coloring, the lignin content of the ligno pulp is preferably 15% by mass or less, more preferably about 7% or less, and more preferably about 5% or less. Is the most preferable.

Examples of the shape of the cellulosic fiber aggregate (pulp, hereinafter also referred to as raw material pulp) used for preparing the defibrating raw material include cotton-like, paper-like, sheet-like, and non-woven fabric-like. When a paper-like, sheet-like or non-woven fabric is used, it is preferable that after chemical modification, it is made into a cotton-like or powder-like material by means such as cutting and crushing, mixed with a resin in advance, and subjected to a defibration treatment step.

The method for preparing the defibrated raw material chemically modified with an acyl group (acyllation reaction) will be described.

Acylation of the raw material pulp with an acyl group can be carried out by a known method, for example, by reacting an acylating agent having an acyl group with the raw material pulp in a solvent with stirring or in a stationary state.

Examples of the acylating agent having an acyl group include carboxylic acid anhydrides, carboxylic acid halides such as carboxylic acid chloride, and carboxylic acid vinyl esters. Among these, vinyl carboxylic acid ester is preferable because it is easy to remove by-products from the reaction system.

In the chemical modification with an acyl group, by using the corresponding carboxylic acid vinyl ester (vinyl carboxylate) as the acylating agent, the chemically modified cellulose-based fiber obtained by acylation is less colored, and this is combined. It is possible to reduce the coloring of the melt-kneaded composition (composite) produced by chemistry.

Of course, acylating agents other than carboxylic acid vinyl esters (for example, carboxylic acid chloride and carboxylic acid anhydride) can also be used. In this case, it is preferable to add an organic base or an inorganic base in order to capture the acid (hydrochloride, carboxylic acid, etc.) produced by the acylation reaction during the reaction. However, the produced salt is likely to be mixed with the acylated cellulosic fiber, and this may cause the target acylated cellulosic fiber to be colored. In this case, it is necessary to carefully purify the fiber.

Among these acylating agents, when an acylating agent having an acyl group selected from the group consisting of an acetyl group, a pivaloyl group, a benzoyl group, a 4-methoxybenzoyl group and a 4-methylbenzoyl group is used. It is preferable because it can produce an acylated microfibrillated cellulose-based fiber having particularly good thermal stability.

Specific examples of the acylating agent having an acyl group include vinyl acetate, acetic anhydride, vinyl pivalate, anhydride pivalic acid, vinyl benzoate, vinyl 4-methoxybenzoate, vinyl 4-methylbenzoate and the like.

Among these, acylating agents having an acetyl group (vinyl acetate and acetic anhydride) are preferable from the viewpoint of production cost.

The acylation reaction is preferably carried out in a solvent in the presence of a base.

As the solvent, a solvent that does not react with the acylating agent, easily swells the acylating raw material, and can be easily removed from the reaction system after the reaction with the acylating raw material is preferable.

Examples of such a solvent include polar aprotic solvents such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), and dioxane. The amount of the solvent used is about 20 to 200 parts by mass with respect to 1 part by mass of the acylated raw material in a dry state.

However, when the acylating agent is a liquid at the reaction temperature and the substance by-produced by the reaction is also a liquid, the acylating agent and the by-product can be used as a solvent. The amount of the solvent used in this case is about 0 to 3 parts by mass with respect to 1 part by mass of the acylated raw material. For example, in the case of acylation (that is, acetylation) using acetic anhydride as an acylating agent, the amount of the solvent used is about 0 (solvent-free) to 3 parts by mass with respect to 1 part by mass of the acylating raw material. is there.

Examples of the base include amines such as pyridine and dimethylaniline; alkali metal salts of acetic acid such as potassium acetate and sodium acetate; and carbonates of alkali metals such as lithium carbonate, potassium carbonate and sodium carbonate. The amount of the base used is about 0.1 to 1 mol with respect to 1 mol of the hydroxyl group in the acylation raw material.

The amount of the acylating agent used for the raw material pulp can be appropriately adjusted depending on the water content of the raw material pulp, the target degree of acylation (degree of substitution, DS), and the like.

For the degree of acylation (substitution degree, DS) during the acylation reaction, the amount required for analysis is collected from the reaction mixture, and then the unreacted acylating agent, acylation by-product, etc. are washed, extracted, etc. After removal, the FTIR spectrum can be measured and quantified using a calibration curve prepared in advance. Therefore, the reaction is stopped when the desired DS is reached, and the reaction mixture is subjected to normal purification operations such as filtration, washing, and extraction to obtain an acylated cellulosic fiber aggregate having the desired DS. (Acylated pulp) can be obtained.

The amount of the acylating agent used is about 0.5 to 2 times the number of moles of hydroxyl groups present in the raw material pulp. When the raw material pulp is in a water-containing state, it is preferable to use a larger amount of the acylating agent than the above in consideration of the amount of the acylating agent consumed by the water.

The reaction temperature is usually about 10 to 120 ° C, preferably about 20 to 100 ° C.

The reaction time is usually about 2 to 24 hours when acylating the raw material pulp derived from wood, and usually about 4 to 100 hours when acylating the raw material pulp derived from fine substances.

4. (B) Vinyl Chloride Polymer The (B) vinyl chloride polymer in the present invention is a homopolymer of vinyl chloride or a combination of vinyl chloride and another vinyl-based monomer copolymerizable with vinyl chloride. Examples include polymers, as well as vinyl chloride, other vinyl-based monomers copolymerizable if necessary, and partially crosslinked vinyl chloride-based polymers by copolymerization with polyfunctional monomers.

Examples of the copolymer of vinyl chloride and other vinyl-based monomers copolymerizable with vinyl chloride include α-monoolefin-based monomers such as ethylene, propylene and butylene; vinyl acetate, vinyl propionate and the like. Vinyl esters; alkyl vinyl ethers such as methyl vinyl ethers and cetyl vinyl ethers; styrene derivatives such as styrene and α-methyl styrene; (meth) acrylic acid esters such as n-butyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate; acrylonitrile, methacrylonitrile. Vinyl cyanide such as nitrile; N-substituted maleimide such as cyclohexyl maleimide and phenyl maleimide; and copolymers of at least one or more of vinylidene such as vinylidene chloride and vinyl chloride can be mentioned.

Further, examples of the partially crosslinked vinyl chloride polymer obtained by copolymerization of vinyl chloride and a polyfunctional monomer include polyfunctionals such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl fumarate, diallyl adipate, and triallyl cyanurate. Allyl compounds; Polyfunctional vinyl ethers such as ethylene glycol divinyl ether and octadecane divinyl ether; 1,3-butylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol At least one or more of polyfunctional monomers copolymerizable with vinyl chloride such as polyfunctional (meth) acrylates such as di (meth) acrylate and trimethylpropantri (meth) acrylate and a copolymer of vinyl chloride are mentioned. It is a vinyl chloride-based polymer that has a partially crosslinked structure.

The average degree of polymerization of the vinyl chloride polymer (B) is 600 or more and 3000 or less. Within such a range, the balance of moldability of the mixture with the defibrating raw material can be improved. Here, when the average degree of polymerization of the vinyl chloride polymer (B) is in the range of 700 or more and 2000 or less, the balance of moldability of the mixture with the defibrating raw material is further improved.

The method for producing the vinyl chloride polymer (B) may be any of a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a bulk polymerization method and the like, and the suspension polymerization method is not particularly limited. It is preferable because there is little residual monomer.

(B) The suspension polymerization method of the vinyl chloride polymer is well known, and a known method may be used, and there is no particular limitation.

5. (C) Ethylene-vinyl acetate-based copolymer The (C) ethylene-vinyl acetate-based copolymer in the present invention is a copolymer of a vinyl ester-based monomer and an ethylene monomer, and is under the following conditions (d) and (e). Meet.
(D) The content of vinyl acetate constituting the (C) ethylene-vinyl acetate-based copolymer is 3% by mass or more and 85% by mass or less.
(E) The acetyl group of vinyl acetate constituting the ethylene-vinyl acetate-based copolymer (C) is replaced with a hydrogen atom by a saponification reaction, and the degree of saponification is 0% or more and 95% or less.

Vinyl ester-based monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caproate, vinyl laurate, vinyl mistylate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, Vinyl ester-based monomers such as vinyl pivalate, vinyl octylate, vinyl monochloroacetate, vinyl adipate, vinyl methacrylate, vinyl crotonic acid, vinyl sorbate, vinyl benzoate, vinyl laurate, and vinyl versatecate can be mentioned. it can. Among these, a homopolymer of vinyl acetate is preferable.

The content of vinyl acetate constituting the (C) ethylene-vinyl acetate-based copolymer is 3% by mass or more and 85% by mass or less, preferably 15% by mass or more and 50% by mass or less. When the content of vinyl acetate is 3% by mass or more, the compatibility with the defibrating raw material is improved, and when it is 85% by mass or less, the strength characteristics of the molded product of the present invention are improved.
The saponification degree of the ethylene-vinyl acetate-based copolymer is 0% or more and 95% or less, preferably 0% or more and 90% or less. When the degree of saponification is 95% or less, compatibility with the defibrating raw material can be exhibited.
From the viewpoint of the strength characteristics of the molded product of the present invention, the content of the (C) ethylene-vinyl acetate-based copolymer is preferably 0.3% by mass or more and 40% by mass or less, preferably 0.5% by mass or more. It is particularly preferably 30% by mass or less.

In the vinyl chloride-based polymer of the present invention, all or part (preferably 10% by mass or more and 90% by mass or less) of the (B) vinyl chloride-based polymer is graft-polymerized with vinyl chloride on the (D) ethylene-vinyl acetate-based copolymer. A vinyl chloride-based copolymer (hereinafter, also referred to as (D) vinyl chloride-based copolymer) is preferable from the viewpoint of the defibability of the defibrating raw material and the strength characteristics of the molded product of the present invention. ..
Further, the vinyl chloride-based polymer (B) in the present invention is a vinyl chloride obtained by copolymerizing (E) vinyl chloride and vinyl acetate in all or part (preferably 10% by mass or more and 90% by mass or less). A based copolymer (hereinafter referred to as (E) vinyl chloride-based copolymer) is preferable from the viewpoint of the defibability of the defibrating raw material and the strength characteristics of the molded product of the present invention.

6. (D) Vinyl Chloride Copolymer The (D) vinyl chloride copolymer in the present invention is a graft copolymer obtained by graft-polymerizing vinyl chloride on the ethylene vinyl acetate copolymer (C). The vinyl chloride-based copolymer (D) is not particularly limited, but polymers having various performances can be obtained depending on the type of ethylene-vinyl acetate-based copolymer used and the vinyl acetate content.

In the vinyl chloride-based copolymer used in the present invention, the ethylene-vinyl acetate-based copolymer constituting the vinyl chloride-based copolymer is the above-mentioned (d) from the viewpoint of compatibility with the defibrating raw material. It is preferable that the requirements of (e) and (e) are satisfied, and the content of the ethylene-vinyl acetate-based copolymer is 0.3% by mass or more and 40% by mass or less from the viewpoint of the strength characteristics of the molded product of the present invention. It is preferably 0.5% by mass or more and 30% by mass or less.

7. (E) Vinyl Chloride Copolymer The (E) vinyl chloride copolymer in the present invention can be obtained by copolymerizing a vinyl chloride monomer and a vinyl acetate monomer at an appropriate ratio.
The (E) vinyl chloride-based copolymer used in the present invention has a vinyl acetate content of 0.3% by mass, which constitutes the (E) vinyl chloride-based copolymer, from the viewpoint of compatibility with the defibrating raw material. % Or more and 30% by mass or less are preferable, and 0.5% by mass or more and 25% by mass or less are particularly preferable.

8. Defibrillation aid In the defibration aid in the present invention, the hydrogen atom of a part of the hydroxyl group of the cellulose fiber is a general formula: R-CO- (in the formula, R is an alkyl group having 1 to 4 carbon atoms, or Indicates a phenyl group that may have an electron-donating substituent.) A defibration aid preferably used for defibrating the defibrating raw material substituted with an acyl group represented by). The following general formula (1): R1-CO-N (R2) -R3 (in the formula, R1 and R3 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or R1 and R3. Together they represent an alkylene group having 3 to 11 carbon atoms; R2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 2 to 4 carbon atoms). It is a defibration aid containing a compound as a main component.

In the defibration aid, in the defibration treatment of the defibration raw material in which the hydrogen atom of a part of the hydroxyl group of the cellulose fiber is replaced with an acyl group, the defibration raw material has the same substituent as the defibration raw material. Helps to be defibrated by the Chemically Modified MFC.

In the general formula (1): R1-CO-N (R2) -R3, R1 and R3 represent the same or different alkyl groups having a hydrogen atom and 1 to 4 carbon atoms, or R1 and R3 are different. Together they represent alkylene groups with 3-11 carbon atoms.

As the alkyl group having 1 to 4 carbon atoms in R1 and R3, a linear alkyl group (methyl, ethyl, n-propyl, and n-butyl) and a branched chain alkyl group (isopropyl, and tert-butyl) are used. Can be mentioned. Of these, a methyl group, an ethyl group, and an n-propyl group are preferable.

Examples of the alkylene group having 3 to 11 carbon atoms formed by combining R1 and R3 include trimethylene, tetramethylene, pentamethylene, and decamethylene, and alkylene groups having 3 to 5 carbon atoms and 9 to 11 carbon atoms. Groups are preferred. In particular, since an amide compound (generic name lactam) having an alkylene group having 3, 5, 10 and 11 carbon atoms is easily available on the market, R1 and R3 are formed together with 3, 5, 10 carbon atoms. And 11 alkylene groups are preferred.

Examples of the alkyl group having 1 to 3 carbon atoms in R2 include a linear alkyl group (methyl, ethyl, and n-propyl) and a branched chain alkyl group (isopropyl). Of these, a methyl group is preferred.

Examples of the acyl group having 2 to 4 carbon atoms in R2 include acetyl and propionyl. Of these, acetyl is preferable.

Specific examples of the amide compound represented by the general formula (1) include N, N-dimethylacetamide, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, and δ-valerolactam. Examples thereof include N-methyl-δ-valerolactam, ε-caprolactam, N-methyl-ε-caprolactam, N-acetyl-ε-caprolactam, undecanlactam and laurolactam.

Among these amide compounds, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, undecanlactam and laurolactam are preferable.

More preferred amide compounds are N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, ε-caprolactam and laurolactam, and the most preferred amide compound is ε-caprolactam.

In addition, the above-mentioned amide compound can also be used as a defibration aid of the present invention by mixing two or more kinds.

When the above defibration aid is used in the vinyl chloride polymer composition of the present invention, it is desirable to add a perchlorate compound in order to suppress discoloration of the molded product.

Examples of the perchlorate compound include lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, magnesium perchlorate, calcium perchlorate, barium perchlorate, ammonium perchlorate and the like. .. Of these, barium perchlorate is preferably used. These perchlorates may be anhydrous or hydrous salts, and may be those dissolved in alcohol-based and ester-based solvents such as butyl diglycol and butyl diglycol adipate, and their dehydrated products. Further, a perchloric acid-containing hydrotalcite obtained by treating hydrotalcite with perchloric acid may be used.

8. A method for defibrating the defibrated raw material and a method for producing a defibrated vinyl chloride-based polymer composition containing the chemically modified MFC.

The vinyl chloride-based polymer composition containing the chemically modified MFC is preferably produced by a method including the following steps (1) to (3).
(1) A step of selecting the defibration raw material and the vinyl chloride composition to be the chemically modified MFC that satisfy the requirements (a) to (c) above after the defibration treatment.
(2) A composition containing the defibrating raw material selected in the step (1), a vinyl chloride-based polymer, an ethylene-vinyl acetate-based copolymer, etc., if necessary (hereinafter, also referred to as the vinyl chloride-based composition). The process of blending
(3) The defibrating raw material blended in the step (2) and the vinyl chloride composition-based polymer are kneaded, and at the same time, the defibrating raw material is defibrated and microfibrillated to form the chemically modified MFC and the chemically modified MFC. A step of obtaining the vinyl chloride-based polymer composition of the present invention containing the vinyl chloride-based composition.

In the step (3) of mixing the microfibrillated chemically modified MFC and the vinyl chloride-based composition, it is preferable to further mix the defibration aid. By mixing the defibration aid, the mixed state of the chemically modified MFC and the vinyl chloride-based composition is improved, and the strength characteristics of the molded product made of the composition of the present invention are improved. The defibration aid may or may not be removed from the mixture of the Chemically Modified MFC and the Vinyl Chloride Composition after the defibration treatment.

As the defibration aid, a defibration aid containing the amide compound represented by the general formula (1): R1-CO-N (R2) -R3 as a main component is preferable.

In the step (3), the composite of the chemically modified MFC and the vinyl chloride-based composition is preferably carried out by a melt-kneading method.

In the melt-kneading step, the defibrating raw material and the vinyl chloride-based composition are melt-kneaded, and the defibrating raw material is defibrated into the chemically modified MFC in the melted vinyl chloride-based composition. This is a step of producing a composition containing a chemically modified MFC and the present vinyl chloride-based composition.

When the vinyl chloride-based polymer composition of the present invention contains an additive other than the defibration aid, it is added in the mixing step of the raw material to be melt-kneaded or in this melt-kneading step, and the defibration material and the chloride are added. It is preferable to melt-knead with the vinyl-based composition.

As the kneader, a uniaxial or multiaxial kneader can be preferably used. It is preferable to increase the rotation speed of the uniaxial or multiaxial kneader to be used because the defibrating raw material of the present invention is likely to be microfibrillated during the melt kneading step.

In this melt-kneading step, the defibration raw material is defibrated by the action of shear stress and a defibration aid during kneading and microfibrillated, and the generated chemically modified MFC suppresses aggregation of fibers and vinyl chloride. It is well dispersed in the system composition.

In this kneading step, the defibrating raw material having a fiber diameter of several tens of μm to several hundreds of μm is defibrated into the chemically modified MFC having a fiber diameter of several tens of nm to several tens of μm during kneading.

The defibration raw material can be combined with the vinyl chloride-based composition while being defibrated by the shear stress of the melt-kneader and the action of the defibration aid during melt-kneading with the vinyl chloride-based composition. Therefore, according to the melt-kneading method, the manufacturing process is simple and the manufacturing cost can be reduced.

The content ratio of the chemically modified MFC in the vinyl chloride polymer composition of the present invention produced by the production method of the present invention is usually 1 mass with respect to the total mass of the chemically modified MFC and the vinyl chloride composition. % Or more and 40% by mass or less, and preferably 3% by mass or more and 30% by mass or less. By setting the content ratio of the chemically modified MFC in the above range, a vinyl chloride-based polymer composition having excellent strength characteristics can be obtained.

The vinyl chloride-based polymer composition of the present invention produced by the production method of the present invention can also be used as a masterbatch. When used as a master batch, the content ratio of the chemically modified MFC is preferably 10% by mass or more and 40% by mass or less with respect to the total mass of the chemically modified MFC and the vinyl chloride-based composition.

The vinyl chloride-based polymer composition of the present invention produced by the production method of the present invention is a composition obtained by melt-kneading the chemically modified MFC and the vinyl chloride-based composition. Since the melt-kneading method is more productive than the method of impregnating the non-woven fabric with the resin or resin precursor solution and the cellulosic fiber to produce a composite, the chemically modified MFC is highly productive by the production method of the present invention. A resin composition containing the above can be produced.

The vinyl chloride-based polymer composition of the present invention may contain additives as long as the effects of the present invention are not impaired. Additives include, for example, compatibilizers, surfactants, starches, polysaccharides such as alginic acid, natural proteins such as gelatin, glue and casein, tannins, zeolites, ceramics, metal powders, calcium carbonate, talc, mica and the like. Examples thereof include inorganic compounds, colorants, plasticizers, flame retardants, processing aids, impact resistance improvers, pigments, heat stabilizers, antistatic agents, ultraviolet absorbers, antioxidants and the like.

9. Molded article The molded article of the present invention can be produced by using the vinyl chloride polymer composition produced by the production method of the present invention. When producing a molded product, a vinyl chloride-based polymer composition processed into various shapes such as powder, sheet, plate, and film can be used as the molding material.

Examples of the molding method include injection molding, mold molding, extrusion molding and the like. Examples of the shape of the molded body include a sheet shape, a plate shape, a film shape, and a three-dimensional structure. Molded bodies having various shapes can be manufactured by the above-mentioned molding method according to the intended use.

By using the vinyl chloride-based polymer composition produced by the production method of the present invention, a molded product having excellent strength characteristics and the like can be obtained.

The molded product produced from the vinyl chloride-based polymer composition produced by the production method of the present invention can be used in fields where mechanical strength (tensile strength, etc.) is required.

Specifically, for example, building materials such as window frames, rain gutters, water and sewage pipes, fittings, drainage basins, and siding materials; interior materials, exterior materials, and structural materials for transportation equipment such as automobiles, trains, ships, and airplanes. Etc .: Can be effectively used as housings, structural materials, internal parts, etc. for electrical appliances such as personal computers, televisions, telephones, and watches. Above all, it can be particularly effectively used as a window frame material, which is preferable.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples.

The meanings of the abbreviations used in Examples and Comparative Examples are as follows.
Ac: Acetyl group TUKP: Unbleached kraft pulp derived from Abies sachalinensis AcTUKP: TUKP in which hydrogen atoms of some hydroxyl groups in TUKP are replaced with acetyl groups.
AcMFTUKP: A fiber in which the hydrogen atom of some hydroxyl groups in TUKP is replaced with an acetyl group and microfibrillated.

In the examples, the component contents of pulp, chemically modified pulp, chemically modified CNF, vinyl chloride resin and the like show parts by mass.

The indication of the chemically modified fiber contained is described by the abbreviation (for example, acetylated Abies sachalinensis unbleached kraft pulp is described by the abbreviation AcTUKP), but the contained mass is converted into the unmodified fiber. (That is, the content mass of AcTUKP is converted to TUKP).

The following terms have the following meanings:
-Pass: The number of times the kneaded material (test material) is supplied to the twin-screw kneader and applied to the kneader is called "pass". Therefore, for example, "1 pass" means that the test material was kneaded once, and "1st pass" means that the test material was first kneaded (as the 1st pass), and "2nd pass". Means that the material that had been kneaded once was then kneaded for the second time.
-Extrusion: It means that the object to be processed (test material) is supplied to a kneader (also called an extruder) and kneaded.

Raw Materials Used In the following examples and comparative examples, the following raw materials were used.
(1) Resin / vinyl chloride (hereinafter referred to as “PVC”): 13% by mass of ethylene-vinyl acetate copolymer manufactured by Taiyo PVC, TH-1000, powdery / vinyl acetate (concentration: 0) content of 26% by mass. A vinyl chloride-based copolymer obtained by graft-polymerizing 87% by mass of vinyl chloride on the contained ethylene-vinyl acetate copolymer (hereinafter referred to as "EVA-G-PVC"): manufactured by Taiyo PVC, both powdered and ethylene-vinyl acetate Polymer (hereinafter referred to as "EVA"): Ethylene-vinyl acetate copolymer and ethylene-vinyl acetate copolymer 90% saponified product (hereinafter referred to as "EVOH") having a vinyl acetate (concentration: 0) content of 42% by mass: 90% saponified vinyl acetate-vinyl acetate-based copolymer of EVA (hereinafter referred to as "VCAC"): Vinyl chloride-based in which 91.1% by mass of vinyl chloride and 8.9% by mass of vinyl acetate are copolymerized. Copolymer (2) Fiber AcTUKP: Unbleached kraft pulp derived from Todomatsu in which the hydrogen atom of some hydroxyl groups is replaced with an acetyl group, DS = 0.86, crystallinity = 81.3%
(3) Defibering aid, ε-caprolactam (4) Additive, Ca-Zn-based composite stabilizer, barium perchlorate (hereinafter, also referred to as "perchlorate")

(Test method and equipment used)
(Observation of defibrated state and dispersed state of fibers in fiber-containing composition with a polarizing microscope)
(A) Preparation of observation sample (1) A test piece of about 2 mm square was cut out from the fiber-containing composition.
(2) A test piece was placed on a slide glass, and a cover glass was placed on the test piece.
(3) The test piece was thinned by pressurizing at 5 MPa for 5 minutes with a press machine heated to 190 ° C.
(4) The sliced sample was immersed in ice water and rapidly cooled to obtain a sample for observation.

(B) Observation The obtained observation sample was observed with an observation device (system polarizing microscope OLYMPUS BX51) at cross Nicol, a temperature of 23 ° C., and a relative humidity of 50%.

(Manufacturing method of molded product)
The obtained vinyl chloride resin composition was kneaded with a roll at a temperature of 185 ° C. for 3 minutes to prepare a roll kneading sheet. The obtained roll-kneaded sheet was press-molded at 185 ° C. under the condition of a pressure of 15 MPa for 20 minutes to prepare a molded product.

(Measuring method of tensile elastic modulus)
Measurements were carried out in accordance with JIS-K7161.

(Measuring method of flexural modulus)
Measurements were carried out in accordance with JIS-K7171.

(Measuring method of storage elastic modulus)
The measurement was carried out in a temperature range of -100 to 200 ° C. and a heating rate of 5 ° C./min.

(Measurement method of thermal conductivity)
Measurements were carried out in accordance with JIS-R1611.

(Measurement method of Vicat softening temperature)
Measurements were performed in accordance with the old JISK6760 ₁₉₈₁ .

(Flame retardant test method)
The test was carried out in accordance with the UL94 vertical flammability test (V-0, 1, 2).

(Measurement method of coefficient of linear expansion)
The scanning range was measured at 0 to 100 ° C., and the inclination was calculated at 0 to 60 ° C.

Example 1
A mixture of AcTUKP, PVC and EVA was melt-kneaded with a twin-screw kneader. Then, PVC was added to the obtained kneaded product and diluted and kneaded to obtain a composition containing AcTUKP, PVC and EVA.

Hereinafter, each step described in FIG. 1 will be described in detail.
(1st pass: melt kneading)
A mixture having a composition ratio of AcTUKP / PVC / EVA / stabilizer = 96.9 / 87/13/5 is melt-kneaded by heating the cylinder temperature to 175 ° C. and passing it through a biaxial kneader equipped with a vent. It was.

The numerical values in the notation (AcTUKP / PVC / EVA / stabilizer = 96.9 / 87/13/5) of the composition ratio of the above mixture subjected to the biaxial kneader have the following meanings.
96.9: The mass ratio of AcTUKP to the total mass of the mixture is shown.
87: The mass ratio of PVC to the total mass of the mixture is shown.
13: The mass ratio of EVA to the total mass of the mixture is shown.
5: The mass ratio of the stabilizer to the total mass of the mixture is shown.

Unless otherwise specified, the description of the composition ratio of the mixture and the kneaded product shall follow this notation method.

(2nd pass: diluted extrusion)
PVC is added to the 1-pass kneaded product to obtain a mixture having a composition ratio of PVC / (the 1-pass kneaded product) = 75/25, which is melt-kneaded (cylinder temperature 175 ° C.) with a twin-screw kneader. The PVC-based polymer composition of Example 1 was obtained. The composition ratio of the obtained PVC-based polymer composition was AcTUKP / PVC / EVA / stabilizer = 10.0 / 83.9 / 1.8 / 4.3.

From the obtained composition, a sample for microscopic observation was prepared according to the above conditions, and the state of the fibers in the sample was observed with the above-mentioned polarizing microscope. The obtained polarizing microscope observation image is shown in FIG. According to the image observed with a polarizing microscope, the fiber diameter of the thick fiber was 20 μm or less, and the fiber was melted without being torn. In addition, an aggregate of fibers having an unclear outline of several tens of nm to several μm was observed as a white mist. In addition, fine fibers with a fiber diameter of several μm were also observed.

Example 2
The PVC-based polymer composition of Example 2 was obtained in the same manner as in Example 1 except that the resin in the first pass was EVA-G-PVC and the cylinder temperature in the first pass was 185 ° C. It was.

Hereinafter, each step described in FIG. 3 will be described in detail.
(1st pass: melt kneading)
A mixture having a composition ratio of AcTUKP / EVA-G-PVC / stabilizer = 96.9 / 100/5 is melt-kneaded by heating the cylinder temperature to 175 ° C. and passing it through a biaxial kneader provided with a vent. It was.

(2nd pass: diluted extrusion)
PVC is added to the 1-pass kneaded product to obtain a mixture having a composition ratio of PVC / (the 1-pass kneaded product) = 75/25, which is melt-kneaded (cylinder temperature 175 ° C.) with a twin-screw kneader. The PVC-based polymer composition of Example 2 was obtained. The composition ratio of the obtained PVC-based polymer composition was AcTUKP / PVC / EVA-G-PVC / stabilizer = 10.0 / 71.8 / 13.9 / 4.3.

From the obtained composition, a sample for microscopic observation was prepared according to the above conditions, and the state of the fibers in the sample was observed with the above-mentioned polarizing microscope. The obtained polarizing microscope observation image is shown in FIG. According to the image observed with a polarizing microscope, the fiber diameter of the thick fiber was 20 μm or less, and the fiber was melted without being torn. In addition, an aggregate of fibers having an unclear outline of several tens of nm to several μm was observed as a white mist.

Example 3
The PVC-based polymer composition of Example 3 was prepared in the same manner as in Example 1 except that the resin of the first pass was EVA-G-PVC and EVOH and the cylinder temperature of the first pass was 170 ° C. Obtained.

Hereinafter, each step described in FIG. 5 will be described in detail.
(1st pass: melt kneading)
A mixture having a composition ratio of AcTUKP / EVA-G-PVC / EVOH / stabilizer = 96.9 / 90/10/5 is heated to a cylinder temperature of 170 ° C. and passed through a biaxial kneader provided with a vent. Melt kneading was performed.

(2nd pass: diluted extrusion)
PVC is added to the 1-pass kneaded product to obtain a mixture having a composition ratio of PVC / (the 1-pass kneaded product) = 75/25, which is melt-kneaded (cylinder temperature 175 ° C.) with a twin-screw kneader. The PVC-based polymer composition of Example 3 was obtained. The composition ratio of the obtained PVC-based polymer composition was AcTUKP / PVC / EVA-G-PVC / EVOH / stabilizer = 10.0 / 80.6 / 3.6 / 1.5 / 4.3. ..

From the obtained composition, a sample for microscopic observation was prepared according to the above conditions, and the state of the fibers in the sample was observed with the above-mentioned polarizing microscope. The obtained polarizing microscope observation image is shown in FIG. According to the image observed with a polarizing microscope, the fiber diameter of the thick fiber was 20 μm or less, and the fiber was melted without being torn. In addition, an aggregate of fibers having an unclear outline of several tens of nm to several μm was observed as a white mist. In addition, fine fibers with a fiber diameter of several μm were also observed.

Example 4
The PVC-based polymer composition of Example 4 was obtained in the same manner as in Example 1 except that the resin of the first pass was PVC and VCAC and the cylinder temperature of the first pass was 185 ° C.

Hereinafter, each step described in FIG. 7 will be described in detail.
(1st pass: melt kneading)
A mixture having a composition ratio of AcTUKP / PVC / VCAC / stabilizer = 96.9 / 38.7 / 61.3 / 5 is heated to a cylinder temperature of 185 ° C. and passed through a biaxial kneader provided with a vent. Melt kneading was performed.

(2nd pass: diluted extrusion)
PVC is added to the 1-pass kneaded product to obtain a mixture having a composition ratio of PVC / (the 1-pass kneaded product) = 75/25, and this is melt-kneaded (cylinder temperature 175 ° C.) with a twin-screw kneader. The PVC-based polymer composition of Example 4 was obtained. The composition ratio of the obtained PVC-based polymer composition was AcTUKP / PVC / VCAC / stabilizer = 10.0 / 77.1 / 8.6 / 4.3.

From the obtained composition, a sample for microscopic observation was prepared according to the above conditions, and the state of the fibers in the sample was observed with the above-mentioned polarizing microscope. The obtained polarizing microscope observation image is shown in FIG. According to the image observed with a polarizing microscope, the fiber diameter of the thick fiber was 20 μm or less, and the fiber was slightly torn but melted. In addition, although the fiber length was short, fine fibers with a fiber diameter of several μm were also observed.

Example 5
A mixture of AcTUKP, PVC, ε caprolactam and water was kneaded in a twin-screw kneader and dehydrated, then the 1-pass mixture was melt-kneaded (in the second pass) and the remaining water was discharged. Then, PVC was added to the obtained kneaded product and melt-kneaded to obtain a composition containing AcTUKP and PVC.

Hereinafter, each step described in FIG. 9 will be described in detail.
(1st pass: dehydration extrusion)
A mixture having a composition ratio of AcTUKP / PVC / ε caprolactam / water / stabilizer = 12.6 / 12.4 / 15/20 / 0.6 was heated at an inclined cylinder temperature of 80 ° C. to 130 ° C., and a vent was provided. Dehydration extrusion was performed by passing through a twin-screw kneader.

(2nd pass: melt kneading)
Kneading extrusion was performed by passing the above 1-pass mixture through a twin-screw kneader whose cylinder temperature was set to 105 ° C. The remaining water and ε-caprolactam were discharged, and the kneaded product was washed with warm water at 80 ° C. for 2 hours. The composition ratio of the kneaded product after washing was AcTUKP / resin = 38/62.

(3rd pass: diluted extrusion)
PVC is added to the above-mentioned two-pass mixture to obtain a mixture having a composition ratio of PVC / (the above-mentioned two-pass kneaded product) = 66.7 / 33.3, and this is melt-kneaded with a twin-screw kneader (cylinder temperature 175 ° C.). ), And the PVC-based polymer composition of Example 5 was obtained. The composition ratio of the obtained PVC-based polymer composition was AcTUKP / PVC / stabilizer = 10.0 / 85.7 / 4.3.

From the obtained composition, a sample for microscopic observation was prepared according to the above conditions, and the state of the fibers in the sample was observed with the above-mentioned polarizing microscope. The obtained polarizing microscope observation image is shown in FIG. According to the polarizing microscope image, the fiber diameter of the thick fiber was 20 μm or less, and the fiber was melted without being torn. In addition, an aggregate of fibers having an unclear outline of several tens of nm to several μm was observed as a white mist.

Example 6
Same as in Example 5 except that the PVC in the first pass was EVA-G-PVC, the cylinder temperature in the second pass was 95 ° C, and the perchlorate was added before the third pass. The PVC-based polymer composition of Example 6 was obtained.

Hereinafter, each step described in FIG. 11 will be described in detail.
(1st pass: dehydration extrusion)
A mixture having a composition ratio of AcTUKP / EVA-G-PVC / ε caprolactam / water / stabilizer = 12.6 / 12.4 / 15/20 / 0.6 is heated by inclining the cylinder temperature to 80 ° C. to 130 ° C. , Dehydration extrusion was performed by passing through a twin-screw kneader provided with a vent.

(2nd pass: melt kneading)
Kneading extrusion was performed by passing the above 1-pass mixture through a twin-screw kneader whose cylinder temperature was set to 95 ° C. The remaining water and ε-caprolactam were discharged, and the kneaded product was washed with warm water at 80 ° C. for 2 hours. The composition ratio of the kneaded product after washing was AcTUKP / resin = 50/50.

(3rd pass: diluted extrusion)
PVC and perchlorate are added to the above-mentioned 2-pass kneaded product to obtain a mixture having a composition ratio of PVC / (the above-mentioned 2-pass kneaded product) / perchlorate = 75/25 / 0.87. A resin composition was obtained by melt-kneading (cylinder temperature 175 ° C.) with a shaft kneader. The composition ratio of the obtained PVC-based polymer composition was AcTUKP / PVC / EVA-G-PVC / stabilizer and perchlorate = 10.0 / 71.7 / 13.9 / 4.4. Regarding the preparation of the molded product, perchlorate was added to the obtained composition at PVC-based polymerization other composition / perchlorate = 100 / 1.5, and the molded product was prepared according to the above conditions.

From the obtained composition, a sample for microscopic observation was prepared according to the above conditions, and the state of the fibers in the sample was observed with the above-mentioned polarizing microscope. The obtained polarizing microscope observation image is shown in FIG. According to the image observed with a polarizing microscope, the fiber diameter of the thick fiber was 20 μm or less, and the fiber was melted without being torn. In addition, an aggregate of fibers having an unclear outline of several tens of nm to several μm was observed as a white mist. In addition, fine fibers with a fiber diameter of several μm were also observed.

Example 7
The operation after 2 passes is the same as in Example 6 except that PVC is added, diluted and kneaded at a cylinder temperature of 130 ° C., and then washed with warm water at 80 ° C., and perchlorate is not added 3 passes before. The PVC-based polymer composition of Example 7 was obtained.

Hereinafter, each step described in FIG. 13 will be described in detail.
(1st pass: dehydration extrusion)
A mixture having a composition ratio of AcTUKP / EVA-G-PVC / ε caprolactam / water / stabilizer = 12.6 / 12.4 / 15/20 / 0.6 is heated by inclining the cylinder temperature to 80 ° C. to 130 ° C. , Dehydration extrusion was performed by passing through a twin-screw kneader provided with a vent.

(2nd pass: melt kneading)
Kneading extrusion was performed by passing the above 1-pass mixture through a twin-screw kneader whose cylinder temperature was set to 95 ° C. The remaining water and ε-caprolactam were discharged, and the composition ratio of the kneaded product after extrusion was AcTUKP / resin (ε-caprolactam remained) = 30/70.

(3rd pass: diluted extrusion)
PVC is added to the above-mentioned two-pass kneaded product to obtain a mixture having a composition ratio of PVC / (the above-mentioned two-pass kneaded product) = 75/25, which is melt-kneaded (cylinder temperature 130 ° C.) with a twin-screw kneader. Further, the resin composition was obtained by washing with warm water at 80 ° C. for 2 hours. The composition ratio of the obtained PVC-based polymer composition was AcTUKP / PVC / EVA-G-PVC / stabilizer = 10.0 / 71.8 / 13.9 / 4.3. Regarding the preparation of the molded product, perchlorate was added to the obtained composition at PVC-based polymerization other composition / perchlorate = 100 / 1.5, and the molded product was prepared according to the above conditions.

From the obtained composition, a sample for microscopic observation was prepared according to the above conditions, and the state of the fibers in the sample was observed with the above-mentioned polarizing microscope. The obtained polarizing microscope observation image is shown in FIG. According to the image observed with a polarizing microscope, the fiber diameter of the thick fiber was 10 μm or less, and the fiber was unbroken without tearing. In addition, an aggregate of fibers having an unclear outline of several tens of nm to several μm was observed as a white mist. In addition, fine fibers with a fiber diameter of several μm were also observed.

Comparative Example 1
The mixture of PVC / stabilizer = 100/5 was melt-extruded (cylinder temperature 175 ° C.) with a twin-screw kneader. The process is shown in FIG.

Comparative Example 2
The mixture of PVC / EVA-G-PVC / stabilizer = 79.8 / 15.4 / 4.8 was melt-extruded (cylinder temperature 175 ° C.) with a twin-screw kneader. The process is shown in FIG.

For Examples 1 to 7 and Comparative Examples 1 to 2, a molded product was prepared from the obtained compositions according to the above conditions, and the tensile elastic modulus and the flexural modulus were measured by the above method. However, in the preparation of the molded products of Examples 6 and 7, perchlorate was added at a composition ratio of resin composition / perchlorate = 100 / 1.5 before roll kneading. The results are shown in Table 1.

Table 1 shows the results of the tensile elastic modulus and the flexural modulus of Examples 1 to 4 and Comparative Examples 1 and 2.

The following was found from the data in Table 1.

The tensile elastic modulus of the molded product produced by the method of Example 1 was 39% higher than that of the molded product made of only PVC (Comparative Example 1), and the flexural modulus was 46% higher.

The tensile elastic modulus of the molded product produced by the method of Example 2 was 34% higher than that of the molded product made of only PVC (Comparative Example 1), and the flexural modulus was 41% higher.

The tensile elastic modulus of the molded product produced by the method of Example 3 was 38% higher than that of the molded product made of only PVC (Comparative Example 1), and the flexural modulus was 46% higher.

The tensile elastic modulus of the molded product produced by the method of Example 4 was 34% higher than that of the molded product made of only PVC (Comparative Example 1), and the flexural modulus was 40% higher.

The tensile elastic modulus of the molded product produced by the method of Example 5 was 48% higher than that of the molded product made of only PVC (Comparative Example 1), and the flexural modulus was 47% higher.

The tensile elastic modulus of the molded product produced by the method of Example 6 was 43% higher than that of the molded product made of only PVC (Comparative Example 1), and the flexural modulus was 57% higher.

The tensile elastic modulus of the molded product produced by the method of Example 7 was 50% higher than that of the molded product made of only PVC (Comparative Example 1), and the flexural modulus was 69% higher.

In Examples 1, 3 and 4, the tensile elastic modulus and the flexural modulus of the molded product both showed high values. It can be seen that this is because EVA, EVOH, and VCAC each promoted the defibration of AcTUKP and brought about the reinforcing effect of the fibers in the PVC-based polymer composition.

Comparing Example 2 and Comparative Example 2, the molded product made of the composition produced by the method of Example 2 (EVA-G-PVC was used in the first pass) was compared with the molded product of Comparative Example 2. , The tensile elastic modulus showed a value 43% higher, and the bending elastic modulus showed a value 44% higher. This shows the reinforcing effect of the fibers, and it can be seen that the PVC-based polymer composition has high rigidity due to the addition of the fibers.

In Example 5, ε caprolactam was added without using EVA-G-PVC to obtain a PVC-based resin composition. ε Caprolactam has the effect of a defibration aid that swells cellulose to improve defibration, the effect of an aggregation inhibitor that suppresses reaggregation of defibrated AcTUKP during kneading, and when diluted with a PVC matrix. It is considered that there is an effect of a dispersant that promotes the dispersion effect of. Therefore, the tensile elastic modulus of the molded product was 10% higher and the flexural modulus was 4% higher than that of Example 2 in which ε-caprolactam was not present.

From the above, it can be seen that the effect of adding εcaprolactam as a defibration accelerator is large.

With respect to Examples 6 and 7, EVA-G-PVC and ε caprolactum, which were found to have a fiber defibration promoting effect in Examples 2 and 5, were used in combination to obtain a tensile elastic modulus and bending elasticity of the molded product. Both rates showed high values.

Comparing Example 6 and Example 7, the removal timing of ε caprolactam after the second pass is different. In Example 6, removal by washing with warm water was performed before 3 passes of dilution and kneading, and in Example 7, εcaprolactam was removed after 3 passes. As a result, Example 7 showed a value 5% higher in tensile elastic modulus and 8% higher value in bending elastic modulus than Example 6.

From the above, it can be seen that the presence of ε caprolactam even during dilution and kneading maintains the fiber defibration promoting effect.

(Vicat softening temperature, thermal conductivity)
For Example 2, Example 6, and Comparative Example 1, the vicut softening temperature and thermal conductivity of the molded product were measured, respectively. The results are shown in the table.

It can be seen that the Vicat softening temperature in Example 2 (addition of AcTUKP and use of EVA-G-PVC) was 20 ° C. higher than that in Comparative Example 1 (PVC only). Further, it can be seen that Example 6 (addition of ε caprolactam in addition to Example 2) is 32 ° C. higher than that of Comparative Example 1.

From the above, it was also confirmed that the reinforcement with fibers improves the rigidity at high temperature. It can also be seen that this effect is enhanced by the defibration of the fibers.

It can be seen that the thermal conductivity has hardly changed in all of Example 2, Example 6, and Comparative Example 1. From this, it was confirmed that the high heat insulating property of the PVC resin composition was maintained.

(Coefficient of linear expansion, flame retardancy)
For Example 6 and Comparative Example 1, the linear expansion coefficient of the molded product was measured and the flame retardancy test was performed, respectively. The results are shown in the table.

Regarding the linear expansion coefficient, Example 6 shows a better linear expansion coefficient as compared with Comparative Example 1, and it can be seen that the dimensional stability is improved.

Regarding flame retardancy, both Example 6 and Comparative Example 1 serve as indicators of V-0, which is the least flammable, indicating that the addition of fibers does not eliminate the self-extinguishing property of PVC.

Claims (7)

A vinyl chloride-based polymer composition containing (A) chemically modified cellulose nanofibers and (B) vinyl chloride-based polymer, wherein the (A) chemically modified cellulose nanofibers are described in the following (a) to (c). ) Is a vinyl chloride polymer composition that satisfies all the conditions.
(A) The crystallinity of the chemically modified cellulose nanofibers (A) is 42.7% or more and 90.0% or less.
(B) The chemically modified cellulose nanofiber (A) has a hydrogen atom of a hydroxyl group of a sugar chain constituting the cellulose nanofiber, which has a general formula: (R-CO-, where R is an alkyl group having 1 to 4 carbon atoms. , Or an acyl group represented by (indicating a phenyl group which may have an electron-donating substituent), and the degree of substitution is 0.56 or more and 2.52 or less.
(C) The cellulose of the chemically modified cellulose nanofibers and cellulose nanofibers (A) is lignocellulose. The vinyl chloride-based weight according to claim 1, further comprising (C) an ethylene-vinyl acetate-based copolymer, wherein the (C) ethylene-vinyl acetate-based copolymer satisfies the following conditions (d) and (e). Combined composition.
(D) The content of vinyl acetate constituting the (C) ethylene-vinyl acetate-based copolymer is 3% by mass or more and 85% by mass or less.
(E) The acetyl group of vinyl acetate constituting the ethylene-vinyl acetate-based copolymer (C) is replaced with a hydrogen atom by a saponification reaction, and the degree of saponification is 0% or more and 95% or less. All or part of the (B) vinyl chloride-based polymer is a vinyl chloride-based copolymer obtained by graft-polymerizing vinyl chloride on the (D) ethylene-vinyl acetate-based polymer, and the (D) vinyl chloride-based polymer. The vinyl chloride-based polymer composition according to claim 1 or 2, wherein the copolymer satisfies the following condition (f).
(F) The ethylene-vinyl acetate-based copolymer constituting the vinyl chloride-based copolymer (D) satisfies the conditions (d) and (e), and the content thereof is 0.3% by mass or more and 40% by mass. % Or less. All or part of the (B) vinyl chloride-based polymer is a vinyl chloride-based copolymer obtained by copolymerizing (E) vinyl chloride and vinyl acetate, and the (E) vinyl chloride-based copolymer is described below. The vinyl chloride-based polymer composition according to claim 1 or 2, which satisfies the condition of (g).
(G) The content of vinyl acetate constituting the vinyl chloride-based copolymer (E) is 0.3% by mass or more and 30% by mass or less. The method for producing a vinyl chloride-based polymer composition according to any one of claims 1 to 4, wherein the vinyl chloride-based polymer composition comprises the following steps (1) to (3). Manufacturing method of things.
(1) Chemically modified pulp and (B) vinyl chloride polymer that satisfy the following requirements (a) to (c) after defibration treatment (A) to become chemically modified cellulose nanofibers, if necessary (C) ) Step of selecting ethylene vinyl acetate copolymer,
(A) The crystallinity of the chemically modified cellulose nanofibers is 42.7% or more and 90.0% or less.
(B) In the chemically modified cellulose nanofiber, the hydrogen atom of the hydroxyl group of the sugar chain constituting the cellulose nanofiber is substituted with an acyl group, and the degree of substitution is 0.56 or more and 2.52 or less.
(C) The cellulose of the chemically modified cellulose nanofibers and cellulose nanofibers is lignocellulose.
(2) A step of blending (A1) chemically modified pulp selected in the above step (1), (B) vinyl chloride-based polymer, and (C) ethylene-vinyl acetate-based copolymer, if necessary.
(3) The chemically modified pulp (A1) blended in the step (2), the vinyl chloride-based polymer (B), and the ethylene-vinyl acetate-based copolymer (C), if necessary, are kneaded and simultaneously (A1). ) A vinyl chloride polymer composition obtained by defibrating a chemically modified pulp and containing (A) chemically modified cellulose nanofibers, (B) a vinyl chloride polymer, and, if necessary, (C) an ethylene vinyl acetate copolymer. The process of obtaining. The step (3) is (F) the following general formula (I).
R1-CO-N (R2) -R3 (I)
(In the formula, R1 and R3 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or an alkylene having 3 to 11 carbon atoms formed by combining R1 and R3. Indicates a group. R ² indicates a defibration aid containing a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 2 to 4 carbon atoms as a main component. The method for producing a vinyl chloride-based polymer composition according to claim 5, further comprising (A1) a step of promoting the defibration of the chemically modified pulp. A window frame material comprising the vinyl chloride-based polymer composition according to any one of claims 1 to 4.