JPH0749492B2 - Cellulose derivative thermoplastic resin composition - Google Patents
Cellulose derivative thermoplastic resin compositionInfo
- Publication number
- JPH0749492B2 JPH0749492B2 JP4673687A JP4673687A JPH0749492B2 JP H0749492 B2 JPH0749492 B2 JP H0749492B2 JP 4673687 A JP4673687 A JP 4673687A JP 4673687 A JP4673687 A JP 4673687A JP H0749492 B2 JPH0749492 B2 JP H0749492B2
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- cellulose derivative
- silica
- weight
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920002678 cellulose Polymers 0.000 title claims description 22
- 239000001913 cellulose Substances 0.000 title claims description 22
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 19
- 239000011342 resin composition Substances 0.000 title claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 125000005372 silanol group Chemical group 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 description 9
- 229910003475 inorganic filler Inorganic materials 0.000 description 9
- 235000019589 hardness Nutrition 0.000 description 8
- 229920002301 cellulose acetate Polymers 0.000 description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- -1 Phthalate ester Chemical class 0.000 description 5
- 235000004415 Burchellia bubalina Nutrition 0.000 description 4
- 240000008537 Burchellia bubalina Species 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- PZBLUWVMZMXIKZ-UHFFFAOYSA-N 2-o-(2-ethoxy-2-oxoethyl) 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCC PZBLUWVMZMXIKZ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- GOJCZVPJCKEBQV-UHFFFAOYSA-N Butyl phthalyl butylglycolate Chemical compound CCCCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCCCC GOJCZVPJCKEBQV-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- HSUIVCLOAAJSRE-UHFFFAOYSA-N bis(2-methoxyethyl) benzene-1,2-dicarboxylate Chemical compound COCCOC(=O)C1=CC=CC=C1C(=O)OCCOC HSUIVCLOAAJSRE-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- RISLXYINQFKFRL-UHFFFAOYSA-N dibutyl nonanedioate Chemical compound CCCCOC(=O)CCCCCCCC(=O)OCCCC RISLXYINQFKFRL-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、無機充填材としてシリカを添加し、耐熱性、
表面硬度および剛性等の物性を向上させたセルロース誘
導体熱可塑性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is characterized by adding silica as an inorganic filler,
The present invention relates to a cellulose derivative thermoplastic resin composition having improved physical properties such as surface hardness and rigidity.
セルロースアセテート、セルロースアセテートプロピオ
ネート、セルロースアセテートブチレート等のセルロー
ス誘導体は、単独で加熱すると溶融と同時に著しく着色
し分解が起こるため、通常適宜な可塑剤の添加により、
流動性を高め熱分解を抑制し、よって成形性に富み、か
つ可撓性、透明性に優れたセルロース誘導体熱可塑性樹
脂とするが、このセルロース誘導体熱可塑性樹脂の適度
な吸湿性を生かし、更に無機充填材や染顔料等を添加し
て不透明にし、感触、風合等をベッ甲、水牛角、象牙に
近くしたものが、装飾品等にそれらの模造品として広く
使用されている。Cellulose acetate, cellulose acetate propionate, cellulose derivative such as cellulose acetate butyrate, when heated alone, because it will be significantly colored and decomposed at the same time when melted, usually by the addition of an appropriate plasticizer,
Cellulose derivative thermoplastic resin that enhances fluidity and suppresses thermal decomposition, is therefore rich in moldability, and has excellent flexibility and transparency. Taking advantage of the appropriate hygroscopicity of this cellulose derivative thermoplastic resin, Inorganic fillers, dyes and pigments, etc. are added to make them opaque, and those having a feeling, touch, etc. close to those of beckles, buffalo horns, and ivory are widely used as imitations for ornaments and the like.
しかしながら、天然素材のベッ甲、水牛角、象牙に比べ
耐熱性、表面硬度等の性能面において不充分であり、セ
ルロース誘導体熱可塑性樹脂の用途拡大の障げとなって
いるのが現状である。However, in comparison with natural materials such as bekko, buffalo horn, and ivory, they are insufficient in heat resistance and surface hardness, which is an obstacle to expansion of applications of the thermoplastic resin of cellulose derivative.
本発明は、分散性、成形性が良く、耐熱性、表面硬度、
剛性等が高い無機充填材含有セルロース誘導体熱可塑性
樹脂組成物を提供するものである。The present invention has good dispersibility, moldability, heat resistance, surface hardness,
Provided is a cellulose derivative thermoplastic resin composition containing an inorganic filler having high rigidity.
本発明者は、上記目的を達成するため種々の無機充填材
について鋭意検討した結果、セルロース誘導体熱可塑性
樹脂に特定の条件を満足するシリカを添加すれば、分散
性、成形性が良く、他の無機充填材よりも補強効果が強
く、耐熱性、表面硬度、剛性等が著しく改善されること
を知見したことに基づき、本発明を完成した。The present inventor has conducted extensive studies on various inorganic fillers to achieve the above object. As a result, when silica satisfying specific conditions is added to a cellulose derivative thermoplastic resin, dispersibility and moldability are improved, and other The present invention has been completed based on the finding that the reinforcing effect is stronger than that of the inorganic filler and the heat resistance, surface hardness, rigidity and the like are remarkably improved.
すなわち、本発明は、セルロース誘導体熱可塑性樹脂10
0重量部に対して、シラノール基数が100平方オングスト
ローム当り3.0以下で、かつBET比表面積が100〜210m2/g
のシリカを10〜40重量部配合してなるセルロース誘導体
熱可塑性樹脂組成物である。That is, the present invention is a cellulose derivative thermoplastic resin 10
0 parts by weight, the number of silanol groups is 3.0 or less per 100 square angstroms, and the BET specific surface area is 100 to 210 m 2 / g.
Is a cellulose derivative thermoplastic resin composition obtained by blending 10 to 40 parts by weight of silica.
本発明に使用されるセルロース誘導体としては、セルロ
ースアセテート、セルロースアセテートプロピオネー
ト、セルロースアセテートブチレートおよび硝酸セルロ
ースなどが挙げられるが、セルロースアセテートが好ま
しい。Examples of the cellulose derivative used in the present invention include cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate and cellulose nitrate, with cellulose acetate being preferred.
このセルロースアセテートには種々の可塑剤が添加され
るが、その代表的なものとしては、ジメチルフタレー
ト、ジエチルフタレート、ジブチルフタレート、ジメト
キシエチルフタレート、エチルフタリルエチルグリコレ
ート、ブチルフタリルブチルグリコレート等のフタル酸
エステル、トリアセチン、ジグリセリンテトラアセテー
ト等のグリセリンエステル、トリフェニルホスフェー
ト、トリクレジルホスフェート等の正燐酸エステル、ジ
ブチルアジペート、ジオクチルアジペート、ジブチルア
ゼレート、ジオクチルアゼレート、ジオクチルセバケー
ト等の二塩基性脂肪酸エステルなどが挙げられ、そのな
かでもジメチルフタレート、ジエチルフタレート、ジブ
チルフタレートが好ましい。可塑剤の添加量としてはセ
ルロースアセテート100重量部に対し、20〜50重量部が
最適であり、20重量部以下では著しく流動性が低下し、
成形温度が高くなり、樹脂の劣化や着色を生じる。ま
た、50重量部以上では流動性は向上するが、樹脂自体が
柔軟になり、硬度向上のためのシリカの添加量が多くな
り、衝撃強度が低下し、成形素材として好ましくない。Various plasticizers are added to this cellulose acetate, and typical ones are dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dimethoxyethyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, etc. Phthalate ester, triacetin, glycerin ester such as diglycerin tetraacetate, orthophosphoric acid ester such as triphenyl phosphate, tricresyl phosphate, dibutyl adipate, dioctyl adipate, dibutyl azelate, dioctyl azelate, dioctyl sebacate, etc. Examples thereof include basic fatty acid esters, and among them, dimethyl phthalate, diethyl phthalate and dibutyl phthalate are preferable. The addition amount of the plasticizer is optimally 20 to 50 parts by weight with respect to 100 parts by weight of cellulose acetate, and if the amount is 20 parts by weight or less, the fluidity is significantly reduced,
The molding temperature becomes high, causing deterioration and coloring of the resin. Further, when it is 50 parts by weight or more, the fluidity is improved, but the resin itself becomes flexible, the amount of silica added for improving the hardness is increased, and the impact strength is lowered, which is not preferable as a molding material.
また、無機充填材としてのシリカは湿式法、乾式法など
各種のものが市販されているが、なかでも本発明の目的
のためには、シラノール基数が100平方オングストロー
ム当り3.0以下で、かつBET比表面積が100〜210m2/gの条
件を満すシリカが良く、このようなシリカとしては、例
えば湿式法により得られる沈殿シリカを加熱処理するこ
とによって製造されたものを挙げることができる。Further, as the inorganic filler, various kinds of silica such as a wet method and a dry method are commercially available. Among them, for the purpose of the present invention, the silanol group number is 3.0 or less per 100 square angstroms, and the BET ratio is Silica satisfying the condition that the surface area is 100 to 210 m 2 / g is preferable, and examples of such silica include those produced by subjecting precipitated silica obtained by a wet method to heat treatment.
ここで、本発明に言うシラノール基数とは熱分析法によ
り求めた値である。すなわち、加熱によりシラノール基
２個が縮合して水分子１個が生成するという脱水反応を
利用し、熱天秤による連続的な減量曲線から算出したも
のである。試料を900℃まで加熱し、150℃を基準として
900℃と150℃間の減量から下記の式より求めた。（但
し、150℃以下の減量は吸着水とした。） A:900℃と150℃間の減量（％） B:150℃以下の減量（％） C:試料のBET比表面積（m2/g） シラノール基数が3.0以上ではシリカ表面のシラノール
基に吸着する水分が多く、この結合水がセルロース誘導
体熱可塑性樹脂に配合し、成形用素材として造粒を行な
う工程において発泡したり、セルロース誘導体の加水分
解を促進したり、また水素結合により粒子間の自己凝集
力が強く働き、セルロース誘導体熱可塑性樹脂中への分
散が不良となるなど多くの問題を生じる。Here, the number of silanol groups referred to in the present invention is a value obtained by a thermal analysis method. That is, it is calculated from a continuous weight loss curve by a thermobalance, utilizing a dehydration reaction in which two silanol groups are condensed by heating to produce one water molecule. Heat the sample to 900 ° C, and use 150 ° C as a reference
It was calculated from the following formula from the weight loss between 900 ° C and 150 ° C. (However, the amount reduced below 150 ° C is assumed to be adsorbed water.) A: Weight loss between 900 ° C and 150 ° C (%) B: Weight loss below 150 ° C (%) C: BET specific surface area of the sample (m 2 / g) When the number of silanol groups is 3.0 or more, it is adsorbed on the silanol groups on the silica surface. There is a lot of water, and this bound water is mixed with the cellulose derivative thermoplastic resin to foam in the process of granulating as a molding material, accelerate the hydrolysis of the cellulose derivative, and self-aggregate between particles by hydrogen bonding. It exerts strong force and causes many problems such as poor dispersion in the cellulose derivative thermoplastic resin.
一方、本発明で言うBET比表面積とは、BET法による窒素
ガス吸着量から求めた比表面積であり、その測定法はAS
TM D−3037に規定されている。このBET比表面積値はシ
リカの基本粒子径の代用値とされ、100m2/g未満では粒
径が荒く、これを配合し成形した場合、平滑な表面なら
びに充分な硬度が得られない。また210m2/gを越える
と、シリカ凝集体同志の凝集力が高くなりすぎ、シリカ
のセルロース誘導体熱可塑性樹脂への分散性が著しく悪
くなる。On the other hand, the BET specific surface area referred to in the present invention is the specific surface area obtained from the nitrogen gas adsorption amount by the BET method, and the measuring method is AS
Specified in TMD-3037. This BET specific surface area value is used as a substitute value for the basic particle diameter of silica, and if it is less than 100 m 2 / g, the particle diameter is rough, and when this is compounded and molded, a smooth surface and sufficient hardness cannot be obtained. On the other hand, when it exceeds 210 m 2 / g, the cohesive force between the silica aggregates becomes too high, and the dispersibility of silica in the thermoplastic resin of the cellulose derivative is significantly deteriorated.
シリカの添加量としては、セルロース誘導体熱可塑性樹
脂100重量部に対して、10〜40重量部が適当であり、10
重量部未満では、補強効果が不充分であり、また40重量
部を越えると著しく流動性が低下し、成形性が悪くな
り、衝撃強度等の物性も悪化する。The amount of silica added is appropriately 10 to 40 parts by weight with respect to 100 parts by weight of the cellulose derivative thermoplastic resin.
If it is less than part by weight, the reinforcing effect is insufficient, and if it exceeds 40 parts by weight, the fluidity is remarkably lowered, the moldability is deteriorated, and the physical properties such as impact strength are deteriorated.
さらに、本発明に用いるシリカとしては、シラン系、チ
タネート系等のカップリング剤などで表面処理したもの
であってもよいが、未処理のものが好ましい。Further, the silica used in the present invention may be surface-treated with a coupling agent such as a silane type or titanate type, but is preferably untreated.
本発明のシリカを配合したセルロース誘導体熱可塑性樹
脂組成物には、この他通常使用されている熱劣化防止の
ための熱安定剤、例えば、弱有機酸、エポキシ化合物、
フォスファイト、チオエーテルフォスファイト、フェノ
ール誘導体、チオフォスファイト、イミダゾール、アミ
ン誘導体、金属石鹸等や染顔料等を通常使用される分量
で適宜添加することができる。In the cellulose derivative thermoplastic resin composition containing silica of the present invention, a heat stabilizer for preventing thermal deterioration which is usually used in addition to the above, for example, a weak organic acid, an epoxy compound,
Phosphite, thioether phosphite, phenol derivative, thiophosphite, imidazole, amine derivative, metallic soap, dyes and pigments, etc. can be appropriately added in the amounts usually used.
本発明の樹脂組成物の製造には、単軸または二軸の混練
押出機、コニーダー、バンバリーミキサーなどの公知の
方法が使用できる。For the production of the resin composition of the present invention, a known method such as a single-screw or twin-screw kneading extruder, a cokneader, a Banbury mixer can be used.
本発明によれば、特定の条件を満足するシリカを配合す
るものであるため、セルロース誘導体熱可塑性樹脂中へ
の分散性が良く成形性に優れ、他の無機充填材より補強
効果が大きく、剛性、耐熱性が高く、表面硬度が天然素
材の象牙、水牛角、ベッ甲に近い優れた特性を有するセ
ルロース誘導体熱可塑性樹脂組成物を得ることができ、
シート、フィルム、パイプ、印材、装飾品、眼鏡枠、工
具柄、食器具側、雑貨など広範囲に利用できるので実用
上価値の高いものである。According to the present invention, since silica that satisfies specific conditions is blended, the dispersibility in the cellulose derivative thermoplastic resin is excellent and the moldability is excellent, the reinforcing effect is greater than other inorganic fillers, and the rigidity is high. , High heat resistance, surface hardness can be obtained ivory of natural materials, buffalo horn, a cellulose derivative thermoplastic resin composition having excellent characteristics close to the bekko,
Since it can be used for a wide range of purposes such as sheets, films, pipes, printing materials, ornaments, eyeglass frames, tool patterns, food utensils, and miscellaneous goods, it is of high practical value.
以下に本発明の実施例及び比較例を示す。 Examples and comparative examples of the present invention will be shown below.
実施例１〜３及び比較例１〜９ セルロースアセテートフレークース（酢化度55.0％，重
合度178,灰分含有量0.043％）100重量部に対し、可塑剤
としてジエチルフタレートを30重量部、熱安定剤として
エポキシ化大豆油0.2重量部およびトリデシルフォスフ
ァイト0.3重量部を加え、さらに第１表に示した無機充
填材をそれぞれ20重量部加え、万能混合撹拌機（三英製
作所製）で良く撹拌、混合し、80℃で４時間乾燥した。
乾燥したコンパウンドを40mmφの小型押出機を用い、22
0℃で溶融、混練後ペレット化した。このペレットを使
用し、流動性（メルトフローインデックス）を測定し
た。また、射出成形機で各種試験片を成形し、物性を比
較評価した。その結果を第１表に示した。第１表に示す
ように本発明による特定のシリカを配合したものは、他
の無機充填材を配合したものより熱変形温度が高く、耐
熱性、剛性（曲げ弾性率）が著しく向上し、また表面硬
度も比較例７〜９に示す天然素材の象牙、水牛角、ベッ
甲に近いセルロース誘導体熱可塑性樹脂組成物が得られ
た。Examples 1 to 3 and Comparative Examples 1 to 9 To 100 parts by weight of cellulose acetate flakes (acetylation degree 55.0%, degree of polymerization 178, ash content 0.043%), 30 parts by weight of diethyl phthalate as a plasticizer, heat stable Add 0.2 parts by weight of epoxidized soybean oil and 0.3 parts by weight of tridecyl phosphite as an agent, and further add 20 parts by weight of each of the inorganic fillers shown in Table 1, and stir well with a universal mixing stirrer (Sanei Seisakusho). , Mixed and dried at 80 ° C. for 4 hours.
Use a 40 mmφ small extruder to dry the compound.
It was melted at 0 ° C, kneaded, and then pelletized. Using these pellets, the fluidity (melt flow index) was measured. In addition, various test pieces were molded with an injection molding machine and the physical properties were comparatively evaluated. The results are shown in Table 1. As shown in Table 1, the one containing the specific silica according to the present invention has a higher heat distortion temperature than those containing the other inorganic fillers, and the heat resistance and the rigidity (flexural modulus) are remarkably improved. The cellulose derivative thermoplastic resin compositions having surface hardnesses similar to those of the natural materials ivory, buffalo horn, and beaker shown in Comparative Examples 7 to 9 were obtained.
Claims (1)
に対して、シラノール基数が100平方オングストローム
当り3.0以下で、かつBET比表面積が100〜210m2/gのシリ
カを10〜40重量部配合してなるセルロース誘導体熱可塑
性樹脂組成物。1. A silica resin having a silanol group number of 3.0 or less per 100 square angstroms and a BET specific surface area of 100 to 210 m 2 / g is mixed with 100 to 40 parts by weight of silica having 100 parts by weight of a cellulose derivative thermoplastic resin. Cellulose derivative thermoplastic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4673687A JPH0749492B2 (en) | 1987-03-03 | 1987-03-03 | Cellulose derivative thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4673687A JPH0749492B2 (en) | 1987-03-03 | 1987-03-03 | Cellulose derivative thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63215744A JPS63215744A (en) | 1988-09-08 |
| JPH0749492B2 true JPH0749492B2 (en) | 1995-05-31 |
Family
ID=12755613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4673687A Expired - Lifetime JPH0749492B2 (en) | 1987-03-03 | 1987-03-03 | Cellulose derivative thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0749492B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970003593B1 (en) * | 1992-09-03 | 1997-03-20 | Samsung Electronics Co Ltd | Projection exposure method and device using mask |
| HU219501B (en) * | 1994-09-16 | 2001-04-28 | Hagedorn Ag. | Procedure and apparatus for manufacturing plasticized celluloze-nitrate |
-
1987
- 1987-03-03 JP JP4673687A patent/JPH0749492B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63215744A (en) | 1988-09-08 |
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