JP4953226B2 - Resin composition and transparent sheet - Google Patents

Description

  The present invention relates to a resin composition excellent in transparency, and further to a transparent sheet obtained by molding the resin composition.

In recent years, it is desired to change to a plastic material derived from biomass because it has little impact on the environment and oil resources will be depleted in the future. In particular, polylactic acid and polyhydroxybutyric acid have attracted much attention as biomass-derived plastics. However, both materials are opaque and are difficult to use as transparent plastics. In addition, since the cellulose skeleton, which is the main component, is derived from biomass, the cellulose derivative has the properties of having a small environmental load and excellent transparency. However, there was a drawback of poor toughness.
As a method for solving these problems, a method of mixing a polyhydroxybutyric acid resin with a cellulose derivative has been proposed (see Non-Patent Documents 1 and 2).
However, in the method of mixing a polyhydroxybutyric acid resin with the cellulose derivative proposed in Non-Patent Documents 1 and 2, it was difficult to stably perform production processing due to the thermal decomposability of polyhydroxybutyric acid. .
Macromolecules, vol. 27, p. 4755 (1994). Journal of Applied Polymer Science, vol. 89, p. 2116 (2003).

  The present invention provides a resin composition of a cellulose derivative that is excellent in transparency and excellent in toughness improvement, and a transparent sheet comprising the resin composition.

The present invention provides (A) a polyepichlorohydrin polymer (excluding epichlorohydrin / ethylene oxide copolymer and epichlorohydrin / ethylene oxide / allyl glycidyl ether terpolymer) "(A) polyepichlorohydrin polymer") 1 to 99% by weight and (B) cellulose derivative 99 to 1% by weight [where (A) + (B) = 100% by weight]. The present invention relates to a resin composition characterized in that it is a component.
Here, the (B) cellulose derivative is cellulose acetate butyrate and / or cellulose acetate propionate, and the total of acetyl content, propionyl content and butyryl content is 40% by weight or more based on (B) cellulose derivative. It is preferable that
Further, the resin composition of the present invention may further contain 1 to 30 parts by weight of a plasticizer with respect to 100 parts by weight of (A) a polyepichlorohydrin polymer and (B) a cellulose derivative. preferable.
Furthermore, the resin composition of the present invention preferably has a haze of a sheet having a thickness of 1 mm of 10 or less.
Furthermore, the resin composition of the present invention preferably has two or more glass transition temperatures observed by dynamic viscoelasticity measurement.
Next, the present invention relates to a transparent sheet obtained by extruding one of the above resin compositions.

  The resin composition of the present invention is obtained by adding a polyepichlorohydrin polymer to a cellulose derivative, and has excellent transparency and toughness. Moreover, when the resin composition of the present invention is used, a transparent sheet having high transparency and excellent toughness can be obtained.

The (A) polyepichlorohydrin polymer used in the present invention is, for example, a homopolymer of epichlorohydrin. In addition, epichlorohydrin and other epoxides such as ethylene oxide, propylene oxide, allyl glycidyl ether And a copolymer thereof. However, the (A) polyepichlorohydrin polymer of the present invention does not include epichlorohydrin / ethylene oxide copolymer and epichlorohydrin / ethylene oxide / allyl glycidyl ether terpolymer. .
The chlorine content of the (A) polyepichlorohydrin polymer is preferably 20% to 38% by weight, more preferably 20% to 26% by weight. The chlorine content is based on chlorine atoms in epichlorohydrin. As the (A) polyepichlorohydrin polymer used in the present invention, a product name epichromer H manufactured by Daiso Corporation, Hyrin H75 manufactured by Nippon Zeon Co., Ltd., which is a homopolymer of epichlorohydrin, is preferable. .

  The cellulose derivative (B) used in the present invention is not particularly limited as long as it is a cellulose derivative, but it is preferable to use cellulose acetate butyrate and / or cellulose acetate propionate because it is excellent in transparency. In order to obtain an excellent transparent material, the total of the acetyl content, propionyl content and butyryl content is preferably 40% by weight or more based on (B) the cellulose derivative. More preferably, it is 40 to 60% by weight. The details of the measurement method such as acetyl content are described in ASTM D817. The average substitution degree of acetate, propionate, and butyrate in cellulose acetate butyrate and / or cellulose acetate propionate is preferably 2.0 or more in total in order to obtain an excellent transparent material.

(B) When cellulose acetate butyrate and cellulose acetate propionate are used in combination as the cellulose derivative, the ratio of the two is 0.01: 99.99 to 99.99: 0.01 in weight ratio.
As the cellulose derivative (B) used in the present invention, cellulose acetate propionate includes trade name CAP-482-20 manufactured by Eastman, and cellulose acetate butyrate is trade name manufactured by Eastman. And CAB-381-20.

  In the resin composition of the present invention, (A) polyepichlorohydrin polymer and (B) cellulose derivative are in a weight ratio of (A) :( B) = 1: 99 to 99: 1, preferably 10:90. ~ 90: 10 (where (A) + (B) = 100 wt%). (A) When the polyepichlorohydrin polymer is less than 1% by weight, heat resistance and transparency are impaired, while when it exceeds 99% by weight, toughness is impaired.

  When the resin composition of the present invention is formed into a sheet having a thickness of 1 mm, the haze measured in accordance with JIS K6714 is 10 or less, preferably 0 to 8, which makes it applicable to various optical materials. It becomes possible. When the haze exceeds 10, the light diffuses and becomes cloudy, which is not suitable for use as a transparent resin.

  Further, the resin composition of the present invention preferably has two or more glass transition temperatures observed by dynamic viscoelasticity measurement, and exhibits excellent heat resistance and toughness due to this property. The measurement of dynamic viscoelasticity can be evaluated with a commercially available dynamic viscoelasticity measuring apparatus. For example, the maximum loss tangent (tan δ) observed when measured at a frequency of 10 Hz under a temperature rising rate of 2 ° C./min. Is defined as the glass transition temperature.

  The resin composition of the present invention contains 1 to 30 parts by weight of a plasticizer, preferably 3 to 100 parts by weight of the total amount of (A) polyepichlorohydrin polymer and (B) cellulose derivative. It is also possible to add 20 parts by weight. The molding process is facilitated by adding a plasticizer.

  Examples of the plasticizer that can be used in the present invention include dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, and di-2-ethylhexyl phthalate. Phthalic acid plasticizers such as di-n-octyl phthalate, diisodecyl phthalate, diisononyl phthalate, dibutylbenzyl phthalate, di-2-ethylhexyl isophthalate, dialkylene glycol phthalates; Ethylhexyl, diisodecyl adipate, dibutyl adipate, dibutyl diglycol adipate, dialkylene glycol adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, triethyl citrate, acetyl citrate Fats such as tributyl Trimellitic plasticizers such as trioctyl trimellitic acid and tridecyl trimellitic acid; pyromellitic plasticizers; tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, triphosphate phosphate Phosphate ester plasticizers such as butoxyethyl; Epoxy plasticizers such as epoxidized soybean oil; Polymer plasticizers such as chlorinated paraffin, polyester polymer plasticizers, and polyether polymer plasticizers 1 type or 2 types or more can be used. As commercial products, Sansizer DOA manufactured by Shin Nippon Rika Co., Ltd., Trimex T-10 manufactured by Kao Corporation, and the like are used.

The method for producing the resin composition of the present invention is not particularly limited, and (A) a polyepichlorohydrin polymer and (B) a cellulose derivative are used as an internal mixer such as a Banbury mixer or a pressure kneader, or a roll kneader. Obtained by mixing using a single screw or twin screw extruder.
When producing the resin composition of the present invention, it is desirable to dry the (A) polyepichlorohydrin polymer and / or (B) the cellulose derivative in advance, and the drying conditions are arbitrary. For example, it is preferable to dry at a temperature of 30 to 90 ° C. for about 30 minutes to 3 days. Also, when molding the resin composition of the present invention, it is desirable to dry the resin composition in advance, and the drying conditions are arbitrary, for example, at a temperature of 30 to 90 ° C. for 30 minutes to It is preferable to dry for about 3 days.

In the resin composition of the present invention, an anti-blocking agent, a release agent, a slip agent, an antifogging agent, a lubricant, a heat stabilizer, an ultraviolet stabilizer, a light stabilizer, a weather stabilizer, an anti-mold, if necessary. An agent, a rust inhibitor, an ion trap agent, a flame retardant, a flame retardant aid, an antistatic agent, an antioxidant, and the like may be included. In particular, in order to improve the antistatic performance, it is preferable to add cationic, anionic and nonionic antistatic agents.
Antistatic agents used in the present invention include lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, dioleyl dimethyl ammonium chloride, stearyl dimethyl ammonium chloride, poly Oxyethylene lauryl dimethyl ammonium perchlorate, polyoxyethylene stearyl dimethyl ammonium perchlorate, stearyl dimethyl 2-hydroxyethylammonium nitrate, oleylaminopropyldimethyl 2-hydroxyethylammonium perchlorate, stearyl oleylaminopropyldimethyl 2 -Hydroxyethylammoni Quaternary ammonium salts such as perchlorate, oleylethyldimethylammonium ethyl sulfate; sodium alkyl sulfonate, sodium sodium alkyl sulfate, alkyl ether sulfate sodium salt, alkyl ether sulfate triethanolamine salt, polyoxyethylene alkyl ether Anionic activators such as sulfate triethanolamine salt, polyoxyethylene alkyl ether sulfate sodium salt, sodium dialkylsulfosuccinate, sodium alkylbenzene sulfonate, sodium acylmethyl taurate, sodium alkyl ether sulfonate; glycerin fatty acid ester, polyglycerin fatty acid ester , Sorbitan fatty acid ester, polyoxyethylene glycerin fat Ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polypropylene glycol fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyoxyethylene alkylphenyl ether, polyethylene glycol, polyethylene glycol / polypropylene glycol block polymer, fatty acid diethanolamide, polyethylene Nonionic activators such as glycol alkylamine and polyethylene glycol alkenylamine; amphoteric activators such as dimethylalkylamine and alkyldiaminoethylglycine sodium, and the like, preferably a cationic activator represented by the following formula (1). These can be used alone or in combination of two or more.

[However, in the formula (1), R1 is an alkyl or alkenyl group, R2 is _CH 3, _CH 2 CH ₃ or _{(C 2 H 4 O) n} H (n,, having 6 to 22 carbon atoms to 10 X represents Cl, ClO ₄ , NO ₃ , CH ₃ SO ₄ , or CH ₃ CH ₂ SO _4. ]

  The addition amount of the antistatic agent is 1 to 20 parts by weight, preferably 2 to 15 parts by weight with respect to 100 parts by weight of the above components (A) to (B). If the antistatic agent is less than 1 part by weight, the antistatic effect is not sufficient. On the other hand, if it exceeds 20 parts by weight, the surface bleeds, becomes sticky, or the sheets are blocked, and the transparency of the sheet is deteriorated. .

  Further, stabilizers that can be added to the resin composition of the present invention include 2,6-di-t-butyl-p-cresol, 2,4,6-tri-tert-butylphenol, n-octadecyl-3- (4′-Hydroxy-3 ′, 5′-di-tert-butylphenol) propionate, styrenated phenol, 4-hydroxy-methyl-2,6-di-tert-butylphenol, 2,5-di-tert-butyl- Hydroquinone, cyclohexylphenol, butylhydroxyanisole, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), 4,4′-isopropylidenebisphenol, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), 1,1-bis- (4 Hydroxyphenyl) cyclohexane, 4,4′-methylene-bis (2,6-di-tert-butylphenol), 2,6-bis (2′-hydroxy-3′-tert-butyl-5′-methylbenzyl) 4-methylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris-methyl-2,4,6-tris (3 5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-3rd Butyl-4-hydroxyphenyl) isocyanurate, tris [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanate, 4,4′-thio Such as bis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), etc. Phenol antioxidants: triphenyl phosphite, tris (nonylphenyl) phosphite, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, tris (tridecyl) phosphite, diphenyl mono (2-ethylhexyl) ) Phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl dipropylene glyco Rudiphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4'-isopropylidenediphenyldiphosphite, trilauryltrithiophosphite, bis (tridecyl) pentaerythritol diphosphite, bis (Nonylphenyl) pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite, etc. Among these antioxidants, phosphite antioxidants are preferable, and tetra (tridecyl) 4,4′-isopropylidene diphenyl diphosphite is more preferable.

The added amount of the stabilizer is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the components (A) to (B). If the amount is less than 0.1 parts by weight, discoloration or the like is caused and the stabilizing effect is poor. On the other hand, if the amount exceeds 5.0 parts by weight, the sheet physical properties are deteriorated and the printability is inferior. More preferably, it is 0.1-2.0 weight part.
Moreover, you may use together a dye and a pigment for the said resin composition for color tone adjustment.

  In addition, as a method of adding the antistatic agent and the like added as necessary to the resin composition, conventionally known methods are used. For example, an internal mixer such as a Banbury mixer or a pressure kneader, a roll It can be obtained by mixing using a kneader, single screw or twin screw extruder.

Furthermore, other thermoplastic resins and rubbers, particularly thermoplastic resins called biodegradable resins, may be blended to such an extent that the performance is not impaired.
As the other thermoplastic resin or rubber, polybutylene succinate, polybutylene succinate adipate or the like can be blended.

The molding method of the resin composition of the present invention is arbitrary, and examples thereof include compression molding, transfer molding, profile extrusion, film, sheet, blow, injection, foaming, extrusion coating, rotational molding and the like. Excellent. When performing sheet forming, it is preferable to set the temperature of the molten resin to 180 ° C. or more because the extrusion load is reduced.
In addition, a multilayer sheet using the resin composition of the present invention for the surface layer by a multilayer coextrusion method using a feed block or a multi-die, etc., and a predetermined thermoplastic resin for the core layer can be molded, The manufacturing method is not limited to these.

  The thickness of the transparent sheet of the present invention is not particularly limited, but is preferably 20 mm or less, more preferably 0.05 to 10 mm, for use in optical materials such as lighting covers and panel display materials for various display devices and interior materials. .

Hereinafter, the present invention will be described with reference to examples, but these are illustrative and the present invention is not limited to these examples.
Various measurements in Examples and Comparative Examples are shown below.
~ Measurement of transparency ~
Based on JIS K6714, the haze of a sheet having a thickness of 1 mm was measured with a haze meter (manufactured by Toyo Seiki Seisakusho, direct-reading type haze meter).
~ Toughness evaluation ~
A sheet having a thickness of 1 mm was cut into a 5 cm square, and a 100 g iron ball was dropped from above to observe the state of the sheet.
~ Evaluation of glass transition temperature ~
A sheet having a thickness of 1 mm was cut into a strip shape, and measured with a forced vibration type dynamic viscoelasticity measuring apparatus (UBM, E4000) at a frequency of 10 Hz and a temperature increase rate of 2 ° C./min. . The temperature at which the loss tangent (tan δ) showed a maximum was taken as the glass transition temperature, and the number of glass transition temperatures was evaluated.

Example 1
80 parts by weight of cellulose acetate propionate (manufactured by Eastman, trade name CAP-482-20, acetyl content 2.5% by weight, propionyl content 46.0% by weight) and epichlorohydrin homopolymer (manufactured by Daiso) , 20 parts by weight of a commercial name Epichromer H, chlorine content of 37% by weight) was mixed for 5 minutes at 200 ° C. and a rotation speed of 30 rpm with an internal mixer (laboratory plast mill, manufactured by Toyo Seiki Seisakusho Co., Ltd.) having an internal volume of 60 cc. The obtained sample was formed into a sheet having a thickness of 1 mm by a small compression molding machine (manufactured by Tester Sangyo) and used for various evaluations. Table 1 shows the formulation and Table 2 shows the results.

Example 2
80 parts by weight of cellulose acetate butyrate (made by Eastman, trade name CAB381-20, acetyl content 13.5% by weight, butyrate content 37% by weight) and epichlorohydrin homopolymer (trade name Epichromer H by Daiso) 20 parts by weight of chlorine content 37% by weight) was mixed for 5 minutes at 200 ° C. and 30 rpm with an internal mixer (laboratory plast mill, manufactured by Toyo Seiki Seisakusho Co., Ltd.) having an internal volume of 60 cc. The obtained sample was molded into a sheet having a thickness of 1 mm by a small compression molding machine (manufactured by Tester Sangyo Co., Ltd.) and used for various evaluations. Table 1 shows the formulation and Table 2 shows the results.

Example 3
A sheet was molded in the same manner as in Example 1 except that the addition amount of cellulose acetate propionate was 70 parts by weight and the addition amount of the epichlorohydrin homopolymer was 30 parts by weight, and used for various evaluations. Table 1 shows the formulation and Table 2 shows the results.

Example 4
A sheet was molded in the same manner as in Example 2 except that the amount of cellulose acetate butyrate added was 70 parts by weight and the amount of epichlorohydrin homopolymer added was 30 parts by weight, and used for various evaluations. Table 1 shows the formulation and Table 2 shows the results.

Example 5
Furthermore, the target mixture was obtained in the same manner as in Example 1 except that 10 parts by weight of diethylhexyl adipate (trade name: Sunsocizer DOA, manufactured by Shin Nippon Chemical Co., Ltd.) was added as a plasticizer, and various evaluations were performed. Table 1 shows the formulation and Table 2 shows the results.

Example 6
Furthermore, the target mixture was obtained in the same manner as in Example 2 except that 10 parts by weight of diethylhexyl adipate (trade name Sansocizer DOA, manufactured by Shin Nippon Chemical Co., Ltd.) was added as a plasticizer, and various evaluations were performed. Table 1 shows the formulation and Table 2 shows the results.

Comparative Example 1
Sheets were prepared only with cellulose acetate propionate used in Example 1, and various evaluations were performed. The formulation is shown in Table 1 and the results are shown in Table 2. It is clear that the toughness is poor.

Comparative Example 2
Although the sheet was produced only with the epichlorohydrin homopolymer used in Example 1, it was difficult to maintain the sheet shape because it was an unvulcanized rubber, and it could not be used as a transparent sheet.
Table 1 shows the formulation and Table 2 shows the results.

Comparative Example 3
A mixture was obtained in the same manner as in Example 1 except that an ethylene / propylene copolymer (manufactured by JSR, EP921) was used instead of the epichlorohydrin homopolymer, and various evaluations were performed. The formulation is shown in Table 1 and the results are shown in Table 2. It is clear that transparency and toughness are poor.

The resin composition of the present invention is suitably used for optical materials such as lighting covers, panel constituent materials for various display devices, and interior materials.

Claims (5)

(A) 1 to 99% by weight of polyepichlorohydrin polymer (excluding epichlorohydrin / ethylene oxide copolymer and epichlorohydrin / ethylene oxide / allyl glycidyl ether terpolymer) (B) Cellulose derivative 99 to 1% by weight [provided that (A) + (B) = 100% by weight] is the main component, and (B) the cellulose derivative is cellulose acetate butyrate and / or cellulose acetate propionate. A resin composition having a total of acetyl content, propionyl content, and butyryl content of (B) 40% by weight or more based on the cellulose derivative . Furthermore, the resin composition of Claim 1 with which 1-30 weight part of plasticizers are mixed with respect to 100 weight part of (A) polyepichlorohydrin polymer and (B) cellulose derivative. The resin composition according to claim 1 or 2, wherein the sheet having a thickness of 1 mm has a haze of 10 or less. The resin composition according to any one of claims 1 to 3, wherein there are two or more glass transition temperatures observed by dynamic viscoelasticity measurement. The transparent sheet obtained by extruding the resin composition of any one of Claims 1-4 .