JPS6119655A - Resin composition for molding - Google Patents
Resin composition for moldingInfo
- Publication number
- JPS6119655A JPS6119655A JP13907884A JP13907884A JPS6119655A JP S6119655 A JPS6119655 A JP S6119655A JP 13907884 A JP13907884 A JP 13907884A JP 13907884 A JP13907884 A JP 13907884A JP S6119655 A JPS6119655 A JP S6119655A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- component
- styrene
- molding
- weight
- 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.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は成形用樹脂およびガラス繊維を主成分とするシ
ート状成形用材料(S、M、0. (シート・モールデ
ィング・コンパウンド))に使用する新規な成形用樹脂
組成物に関する。Detailed Description of the Invention (Industrial Application Field) The present invention is used for sheet molding materials (S, M, 0. (sheet molding compounds)) whose main components are molding resins and glass fibers. The present invention relates to a novel molding resin composition.
(従来の技術)
一般に、不飽和ポリエステル樹脂(以下UPと略称する
)を使用、したシート状成形用材料においては、成形収
縮率が10チ近くもあるために実用に供するにはポリス
チレン、ポリ酢酸ビニルなどの熱可塑性樹脂を「低収縮
剤」として添加している。この場合でも、(イ)製造上
の観点においてUPと低収縮剤とが分離して不均一な系
を生ずることや、混合時粘度が高いなど、および(ロ)
性能上の観点において低収縮化が不十分なために成形部
表面のガラス繊維が浮き出すことによる「小さなうねり
」を多く生ずることや、加圧成形時の流動特性が適当で
ないことに基因するリプ、ボス部のヒケ、および不均一
な分散による「太きなうねシ」を生ずるなどの欠陥が十
分に改善されるに至っていない。(Prior art) In general, sheet-form molding materials using unsaturated polyester resin (hereinafter abbreviated as UP) have a molding shrinkage rate of nearly 10 inches, so polystyrene, polyacetic acid, etc. are not suitable for practical use. Thermoplastic resins such as vinyl are added as "low shrinkage agents." Even in this case, (a) UP and low shrinkage agent may separate from each other from a manufacturing standpoint, resulting in a non-uniform system, or the viscosity during mixing may be high, and (b)
From a performance standpoint, low shrinkage is insufficient, resulting in many "small waviness" caused by the protrusion of glass fibers on the surface of the molded part, and rippling caused by inappropriate flow characteristics during pressure molding. Defects such as sink marks on the boss, and "thick ridges" due to non-uniform dispersion have not been sufficiently improved.
例えば、自動車外板用のような高度の表面性が要求され
る成形物品を得るには上述する要因をすべて改善する必
要がめる。この目的を達成するために種々の組成を有す
る樹脂が開発されてはいるが、いずれの樹脂も一長一短
の特徴を有している。For example, in order to obtain molded articles that require a high degree of surface quality, such as those used for automobile exterior panels, it is necessary to improve all of the above-mentioned factors. Although resins having various compositions have been developed to achieve this purpose, each resin has its own advantages and disadvantages.
例えば、上記目的に、更に耐衝撃性の向上を付加するた
めに低収縮剤としてスチレン−ブタジェン−スチレン
ブロック共重合体(以下SBSと略称する)、例えば商
品名[クレイトンDX −1800Jお工び[クレイト
ンGX−1855J (シェル化学C株)製)を単独、
で使用した組成物が開発されている。For example, for the above purpose, styrene-butadiene-styrene is used as a low shrinkage agent to further improve impact resistance.
A block copolymer (hereinafter abbreviated as SBS), for example, the product name [Krayton DX-1800J [Krayton GX-1855J (made by Shell Chemical Co., Ltd.)] alone,
A composition has been developed for use in
この場合、SBSは、いわゆる、熱可塑性エラストマー
であり、ポリメチレン ブロックを有することにぶり熱
可塑性を示し、またポリブタジェンブロックによシェラ
ストマーの性質を有してお9、このためにSBSを低収
縮剤として使用する場合に。In this case, SBS is a so-called thermoplastic elastomer, which exhibits thermoplasticity due to its polymethylene block, and has shellastomer properties due to its polybutadiene block9, which makes SBS less When used as a shrinking agent.
は他の低収縮剤に比べて熱時の流動性が改良されること
から「太きなうねシ」の少ない成形物が得られるが、し
かし成形収縮率が十分に小さくならず、それ故「小さな
うね9」や鮮映性に乏しい成 4形物が形成することに
なる。更に、またSBSを低収縮剤として使用する場合
にはコレパウンド製。Compared to other low-shrinkage agents, it has improved fluidity during heating and can produce molded products with fewer "thick ridges," but the molding shrinkage rate is not sufficiently small, so This results in the formation of "small ridges 9" and artifacts with poor image clarity. Furthermore, if SBS is used as a low shrinkage agent, it is manufactured by Collepound.
造時において高粘度であること、SBSとUPとが実質
的に非相溶であるためにSMO化した際の分離による不
均一化が表面平滑性を悪くすること、および比較的に極
性の小さいSBSを分散するために塗料密着性および接
着性を悪くすることなど種々の問題点があった。It has a high viscosity at the time of manufacturing, SBS and UP are substantially incompatible, so the unevenness caused by separation during SMO formation deteriorates the surface smoothness, and it has relatively low polarity. There have been various problems such as poor paint adhesion and adhesion due to the dispersion of SBS.
(問題点を解決するための手段)
本発明は上述するような従来の問題点に着目し7て鋭意
研究の結果、特定の組成物成分を用いることによって表
面平滑性、寸法安定性および塗料密着性の優れ念新規な
成形用樹脂組成物を開発したものである。(Means for Solving the Problems) The present invention focuses on the above-mentioned conventional problems, and as a result of extensive research, the present invention improves surface smoothness, dimensional stability, and paint adhesion by using specific composition components. We have developed a new molding resin composition with excellent properties.
本発明の成形用樹脂組成物Fi(4)不飽和ポリエステ
ル樹脂、中)スチレン−ブタ・ジ゛エンースチレンブロ
ック共重合体、(C)ポリカプロラクトンおよび■)共
重合可能な単量体の4成分からなることを特徴としてい
る。Molding resin composition Fi of the present invention (4) unsaturated polyester resin, middle) styrene-butadiene-styrene block copolymer, (C) polycaprolactone, and (1) copolymerizable monomer 4 It is characterized by consisting of ingredients.
本発明において用いる(4)成分の不飽和ポリエステル
樹脂(UP)は従来普通に用いられている方法によシ得
られる、樹脂であシ、例えばα、β−不飽和二塩基酸お
よび/またはこれと飽和二塩基酸との混合物を多価アル
コールとGO,N2ガスの如き不活性ガス気流中150
−2FlO℃に加熱、脱水重縮合せしめ、生ずる水の除
去と共に温度を徐々に上昇させ、酸価が5〜50の範囲
で重合して得ることができる。勿論、エステル交換反応
のような他の方法を用いて得ることもできる。この方法
において用いられるα、β−不飽和二塩基酸としては、
例えばマレイン酸、ハロゲン化マレイン酸、フマル酸、
7トラコン酸、イタコン酸、およびこれらの無水物を挙
げることができる。iた、飽和二塩基酸としてはフタル
酸、無水フタル酸、テトラヒドロ無水フタル酸、メチル
化テトラヒドロ無水フタル酸、イソフタル酸、テレフタ
ル酸、アジピン酸、グルタル酸、セパ7ン酸などを挙げ
ることができる。また、多価アルコールとしてはエチレ
ングリコール、ジエチレングリコール、ネオペンチルグ
リコール、水添ビスフェノール、l、6−ヘキサンジオ
ールなどを挙げることができる。The unsaturated polyester resin (UP) as component (4) used in the present invention is a resin obtained by a conventionally commonly used method, such as an α,β-unsaturated dibasic acid and/or and a saturated dibasic acid with a polyhydric alcohol and GO, in a stream of an inert gas such as N2 gas at 150 °C.
It can be obtained by heating to -2FlO°C for dehydration polycondensation, and gradually increasing the temperature while removing the resulting water, and polymerizing to an acid value in the range of 5 to 50. Of course, it can also be obtained using other methods such as transesterification. The α,β-unsaturated dibasic acids used in this method include:
For example, maleic acid, halogenated maleic acid, fumaric acid,
7 Traconic acid, itaconic acid and their anhydrides may be mentioned. In addition, examples of saturated dibasic acids include phthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, methylated tetrahydrophthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, glutaric acid, sepa-7nic acid, etc. . Further, examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, neopentyl glycol, hydrogenated bisphenol, and 1,6-hexanediol.
本発明においC用いるCB)成分のスチレン−ブタジェ
ン−スチレン ブロック共重合体(SBS)としては、
例えば商品名「クレイトンDI−1800J および「
クレイトンGX−1855J (シェル化学(株)與)
などを挙げることができ、また(0)成分のポリカプロ
ラクトン(POL )としては6=カプロラクトンを開
環重合して得る分子量1,000〜50,000の線状
重合体を包合するが、一部または全部の末端を−(30
DH化したもの、またはビニル性二重結合を導入したも
のも用いることができる。The styrene-butadiene-styrene block copolymer (SBS) used as the component CB) used in the present invention is as follows:
For example, the product names "Clayton DI-1800J" and "
Clayton GX-1855J (Shell Chemical Co., Ltd.)
Component (0) polycaprolactone (POL) includes a linear polymer having a molecular weight of 1,000 to 50,000 obtained by ring-opening polymerization of 6=caprolactone. -(30
A DH compound or a vinyl double bond-introduced compound can also be used.
更に、本発明において用いる(6)成分の共重合可能な
単量体としては(1)成分の不飽和ポリエステル樹脂と
共重合し、架橋剤として用いることのできる単量体、゛
例えばスチレン、ノ・ロゲン化スチレン、ビニルトルエ
ン、ジビニルベンゼンなどを挙ケることができる。Further, as the copolymerizable monomer of component (6) used in the present invention, monomers that can be copolymerized with the unsaturated polyester resin of component (1) and used as a crosslinking agent, such as styrene, etc. - Examples include logenated styrene, vinyltoluene, divinylbenzene, etc.
本発明の樹脂組成物においては、上記(4)成分の01
’ 20〜60重量部に対して上記の)成分のSBSと
(C1成分のPOLとをその合計で5〜80重量部、た
ソしSBS/POL比が0.07〜7になるように配合
する。更に、上記(’l+sBs+POL )の8成分
合鼾を100重量部としての)成分の共重合可能な単量
体を60〜145重量部の割合で配合する。■)成分が
60重量部以下ではコンパウンド粘度が高くな9製造上
混練に困難が生じたシ、またガラスの濡れが悪くな9、
更に成形時の流動性が低下する。In the resin composition of the present invention, 01 of the above component (4)
'For 20 to 60 parts by weight, the SBS (above) component and the POL (C1 component) are combined in a total of 5 to 80 parts by weight, so that the SBS/POL ratio is 0.07 to 7. Furthermore, monomers that can be copolymerized with the above-mentioned components ('l+sBs+POL) (assuming the total of the eight components is 100 parts by weight) are blended in a proportion of 60 to 145 parts by weight. ■) If the component is less than 60 parts by weight, the viscosity of the compound will be high (9) Difficulty in kneading may occur during production, and glass wetting may be poor (9)
Furthermore, fluidity during molding is reduced.
また、145重量部以上では強度が著しく低下し、塗装
後のグリス、ター発生頻度が高くなり望゛ま゛しくない
。Moreover, if it exceeds 145 parts by weight, the strength will drop significantly and the frequency of occurrence of grease and tar after coating will increase, which is not desirable.
(4)成分が20重量部以下では機械的強鼓や剛性の低
下が著しくなり実用に供することができなくなシ、iた
60重量部以上では相対的に低収縮剤量を減少すること
になるために十分な低収縮効果が得られなくなる。甘た
、Q3)成分/(0)成分(SBS/POL )比が0
.07以下では03)成分と(0)成分との相乗効果が
得られなくなり、十分な低収縮率を示さ表くなる。更に
、熱時の流動性が高くなり、均質々ガラス分散を有する
成形物が得難くなる。一方、かかる比が7以上ではの)
成分と(0)成分との相乗効果が得られなくなると共に
、コンパウンド粘度が高くなジ混練を困難にし、また充
填剤やガラス繊維の濡れが悪化する。(4) If the component is less than 20 parts by weight, mechanical stiffness and a decrease in rigidity will be significant, making it impossible to put it into practical use. As a result, a sufficient low shrinkage effect cannot be obtained. Sweet, Q3) component/(0) component (SBS/POL) ratio is 0
.. If it is less than 07, the synergistic effect of component 03) and component (0) will not be obtained, and a sufficiently low shrinkage rate will be exhibited. Furthermore, the fluidity when heated becomes high, making it difficult to obtain a molded product having homogeneous glass dispersion. On the other hand, if this ratio is 7 or more)
A synergistic effect between the components and component (0) cannot be obtained, and the viscosity of the compound is high, making di-kneading difficult, and wetting of fillers and glass fibers becomes worse.
上述する(4)、ω)、 (0)およびの)の4成分を
配合して得た本発明の成形用樹脂組成物はt−ブチルパ
ーオキシベンゾエート、ジ−t−ブチルパーオキシ−8
,8,5−) IJメチルシクロヘキサン、ベンゾイル
パーオキサイドの如き加熱硬化用有機過酸化物、アゾ
ビスインブチロニトリルの如きラジカルを発生しうるア
ゾ化合物などの1種または2種以上の重合触媒を(4)
成分の不飽和ポリエステル樹脂に対して約0.1〜0.
5重量%の割合で配合して硬化することができる。The molding resin composition of the present invention obtained by blending the four components (4), ω), (0) and ) described above contains t-butylperoxybenzoate, di-t-butylperoxy-8
, 8, 5-) One or more polymerization catalysts such as organic peroxides for heat curing such as IJ methylcyclohexane and benzoyl peroxide, and azo compounds capable of generating radicals such as azobisinbutyronitrile are used. (4)
Approximately 0.1 to 0.0% based on the component unsaturated polyester resin.
It can be cured by blending it in a proportion of 5% by weight.
更に・上述する本発明の樹脂組成物を用いてシート状成
形用材料(SMO)を製造する場合には、樹脂組成物に
増粘剤として、例えば酵化マグネシウム、水酸化マグネ
シウム、酸化カルシウム、水酸化カルシウムがどの1゛
種または2種以上の金属酸化物または金属水酸化物;充
填剤として、例えは炭酸カルシウム、クレー、ガラス粉
、タルクなどの無機粉体(配合量:樹脂組成物100f
i量部に対して100〜250重量部);および強化繊
維として、例えば12.7〜88.1 mm (0,5
〜1.5インチ〕に切断さ5れたガラス繊維、炭素繊維
、有機繊維など;また、更に内添離星剤として、例えば
ステアリン酸亜鉛、ステアリン酸カルシウムなどを配合
し、この配合物を従来において通常使用されているSM
Cマシンなどによシシート化してSMOを形成すること
ができる。更に、形成されたSMO’を80〜40℃で
24〜72時間にゎたシ熟成し、適当な大きさに切断し
、積層して高温(120〜170℃)加圧成形して成形
物を得ることができる。Furthermore, when producing a sheet-like molding material (SMO) using the resin composition of the present invention described above, the resin composition may be added with a thickener such as fermented magnesium, magnesium hydroxide, calcium oxide, water, etc. Calcium oxide is one or more metal oxides or metal hydroxides; as fillers, for example, inorganic powders such as calcium carbonate, clay, glass powder, talc (compounding amount: 100 f of resin composition)
(100 to 250 parts by weight based on i part); and as reinforcing fibers, for example, 12.7 to 88.1 mm (0.5
Glass fibers, carbon fibers, organic fibers, etc. cut into pieces of ~1.5 inches; and further added with an internal separating agent such as zinc stearate, calcium stearate, etc. Usually used SM
The SMO can be formed by sheeting using a C machine or the like. Furthermore, the formed SMO' is aged at 80 to 40°C for 24 to 72 hours, cut into appropriate sizes, laminated and pressure molded at high temperature (120 to 170°C) to form a molded product. Obtainable.
本発明は上述する(4)、 (B)、 (0)およびΦ
)の4成分からなる成形用樹脂組成物の#なかに、これ
ら傷成分に■)成分としてポリスチレンとポリカプロラ
クトンまたはポリ酢酸ビニルまたは飽和ポリエステルと
のブロック−またはグラフト共重体の、またはこの共重
合体の末端を酸変性した重合体のスチレン溶液を配合し
た成形用樹脂組成物を包含する。The present invention relates to the above-mentioned (4), (B), (0) and Φ
) A block or graft copolymer of polystyrene and polycaprolactone or polyvinyl acetate or saturated polyester, or a copolymer thereof, is added to these flawed components in #) of a molding resin composition consisting of four components. This includes a molding resin composition containing a styrene solution of a polymer whose terminal end has been modified with an acid.
このスチレン溶液は上記(7k)、 (B)、 (0)
お工びの)の4成分100重量部に対して約0.5〜l
O重量部の割合で添加する。この添刀口によってUP(
A成分)−8BS(B成分) −POL(O成分)の相
容性を更に改善でき、極めて均質な樹脂組成物を得るこ
とができることを確めた。特にUIP(A成分)として
イソフタル酸系のUPを用いる場合には上記(ト))成
分を含む樹脂組成物を1液タイプとして供することがで
き・特に優れた成形物を得ることができる。This styrene solution is the above (7k), (B), (0)
Approximately 0.5 to 1 liter per 100 parts by weight of the four ingredients
It is added in a proportion of 0 parts by weight. UP (
It was confirmed that the compatibility of component A)-8BS (component B) and POL (component O) could be further improved and an extremely homogeneous resin composition could be obtained. In particular, when isophthalic acid-based UP is used as UIP (component A), the resin composition containing the component (g) above can be provided as a one-component type, and particularly excellent molded products can be obtained.
上記[有])成分を含む樹脂組成物を用いてシート状成
形用材料(SMO)を製造する場合には、樹脂組成物に
ハイドロキノンなどの重合禁止剤をZOO〜zooop
pm添加し、これに充填剤および離型剤を高剪断力を有
する攪拌機を用いて徐々に混合して粘稠なコンパウンド
とした後、増粘剤を添刀口し、更に数分間攪拌する。得
られた配合物を上述するようにSMCマシンなどを用い
てシート化してSMQを形成することができる。更に、
形成されたSMOを上述すると同様にして成形物を成形
することができる。When producing a sheet-shaped molding material (SMO) using a resin composition containing the above-mentioned component, a polymerization inhibitor such as hydroquinone is added to the resin composition by ZOO~zooop.
After gradually mixing the filler and mold release agent using a stirrer with high shear force to form a viscous compound, a thickener is added and the mixture is further stirred for several minutes. The resulting formulation can be sheeted to form SMQ using an SMC machine or the like as described above. Furthermore,
The formed SMO can be molded into a molded article in the same manner as described above.
次に1本発E!Aを実施例について説明する。Next one shot E! A will be explained with reference to an example.
(実施例1)
(1) ’(A)成分として中皮応性イソフタル酸系
不和ポリエステル(商品名1日本ユビカ?5’95J日
本ユピカ(株)製)65重量部を、ハイドロキノン0・
OIM量部全部全溶解(D)成分としてのスチレンモノ
マ=(日本ユビカ(株)製)85重量部に溶解した溶液
を作った(この溶液を「UP=IJ ト称fる)。(Example 1) (1) As component (A), 65 parts by weight of mesothelial-responsive isophthalic acid-based undyed polyester (trade name 1 Nihon Ubika? 5'95J manufactured by Nippon Upika Co., Ltd.), 0.
A solution was prepared in which 85 parts by weight of styrene monomer (manufactured by Nippon Yubika Co., Ltd.) as component (D) was dissolved (this solution was referred to as "UP=IJ").
(2) (B33成として商品名「クレイトノDX−
IBOOJ (シェル化学(株)製)を上記と同様に0
))成分のスチレンモノマーに溶解した80%溶液を作
った(この溶液をrsBs−1」と称する)。(2) (As a B33 product, the product name is “Claytono DX-”)
IBOOJ (manufactured by Shell Chemical Co., Ltd.) was added to 0 in the same manner as above.
)) component was dissolved in styrene monomer to make an 80% solution (this solution is referred to as "rsBs-1").
(8) <a>成分として分子15000〜1000
0で末端−000H変性酸化したPOL 40重量部を
上記と同様にの)成分のスチレンモノマーに溶解した溶
液を作った(この溶液を[P(3L−IJと称する)。(8) 15,000 to 1,000 molecules as <a> component
A solution was prepared by dissolving 40 parts by weight of POL which had been modified and oxidized with -000H at the terminal in the same manner as above in the styrene monomer component (this solution was referred to as [P(3L-IJ)).
生成1.*各港液rUP−1J、 rsBs−11オz
ヒ1’−POL−IJを表IK示す配合量で配合する試
験を行った。試験溝工ではl’−UP−IJ、 rsB
s−IJおよび「pcb−IJをそれぞれ表1に示す配
合量で配合して本発明の樹脂組成物を調製した。同時に
、比較の目的のために、試験iffでは[pcr、−I
Jを配合しないで、また試験/I6mでは[5Bs−I
Jを・配合しないで比較樹脂組成物を調製した。Generation 1. *Each port liquid rUP-1J, rsBs-11oz
A test was conducted in which H1'-POL-IJ was blended in the amounts shown in Table IK. For test trench work, l'-UP-IJ, rsB
The resin composition of the present invention was prepared by blending s-IJ and "pcb-IJ in the amounts shown in Table 1. At the same time, for the purpose of comparison, [pcr, -I
J was not added, and in test/I6m, [5Bs-I
A comparative resin composition was prepared without blending J.
表 エ
上述するように調製した試験ム工の本発明の樹脂組成物
(I)および試験、%Ilおよび■の比較樹脂組成物(
If)および(II)を用い、これらの各組成物に表2
に示す配合量のベンゾエート、ステアリン酸亜鉛、rR
化マグネシウム、炭酸カルシウムおよびガラス繊維を配
合し、これらの各配合物をSMOマシンを用いてシート
化してSMOを形成した。Table E Resin composition of the present invention (I) of the test composition prepared as described above and comparative resin composition of test, %Il and ■
If) and (II), Table 2 is applied to each of these compositions.
Benzoate, zinc stearate, rR in the amounts shown in
Magnesium chloride, calcium carbonate, and glass fiber were blended and each of these blends was sheeted using an SMO machine to form an SMO.
表 2
*コンパウンドに対する重量%
ガラス繊維長: 25mm X 12 /lamφ上記
表2に示す試験4I〜■において得た各SMOを40℃
で48時間にわたり熟成し、増粘粘度を2〜8X10C
pSにした。この増粘した各SMCを140〜145℃
で70 kg/cmにて刀口圧成形して成形物を得た。Table 2 *Weight % with respect to compound Glass fiber length: 25 mm
Aged for 48 hours at
I made it pS. This thickened SMC was heated to 140-145°C.
A molded product was obtained by performing knife press molding at 70 kg/cm.
各成形物の物性について測定し、これらの測定結果を表
8に示す。The physical properties of each molded product were measured, and the measurement results are shown in Table 8.
表 8
*塗料密着性は各成形物をトリクレンで払拭後、焼付タ
イプのエポキシ系プライマーを吹付塗装し・160℃、
80分間の条件で焼付け、硬化せしめた後、この表面を
カッターで十文字に切りつけ交叉部において塗料の浮き
上シの有無、塗料被膜が容易に剥落するか否かで判定し
た。Table 8 *Paint adhesion was determined by wiping each molded item with Triclean, then spray painting with a baking type epoxy primer at 160°C.
After baking and curing for 80 minutes, the surface was cut in a cross pattern with a cutter and judged by whether the paint was lifted at the intersections and whether the paint film peeled off easily.
上記表8から、試験Anおよび■の比較樹脂組成物から
得られた成形物は収縮率が大きく、また試験Allでは
「小さなうね9」が多く生じ1また試験/16. mで
は「太きなうね9jが比較的に多く生ずるという欠点の
あることがわかる。これに対して、試験AIの本発明の
樹脂組成物では成形時の収縮率がマイナス(膨張)であ
υ、しかも「太きなうねカ」および「小さなうねり」と
も全く生ずることなく、表部平滑性が極めて優れた成形
物が得られることがわかる。更に、本発明の樹脂組成物
ではポリカプロラクトン(POL )を用いたことによ
り塗装密着性も優れていることがわかる。From Table 8 above, the molded products obtained from the comparative resin compositions of Tests An and ■ had a large shrinkage rate, and in Test All, many "small ridges 9" were observed in Test 1 and Test/16. It can be seen that "m" has a drawback in that a relatively large number of thick ridges 9j are produced.On the other hand, the resin composition of the present invention in Test AI has a negative shrinkage rate (expansion) during molding. It can be seen that a molded product with extremely excellent surface smoothness was obtained, with no "thick undulations" or "small undulations" occurring at all. Furthermore, it can be seen that the resin composition of the present invention has excellent paint adhesion due to the use of polycaprolactone (POL).
また、更に本発明において上記試験に関連して広範囲に
わたυ彼奴縮化について研究したところ、SBSや5B
−R(スチレン−ブタジェン共重合体)藩どの実質的に
UPと非相容の低収縮剤と、飽和ポリエステルやポリカ
プロラクトンな°どのUPと相溶の低収縮剤とを併用す
ることによってそれぞれの低収縮効果を更に高めること
ができ、著しい相乗効果を発揮する優れた樹脂組成物が
得られることを確めた。In addition, in the present invention, we conducted a wide range of research on υher reduction in connection with the above test, and found that SBS and 5B
-R (styrene-butadiene copolymer) is used in combination with a low-shrinkage agent that is substantially incompatible with UP, and a low-shrinkage agent that is compatible with UP, such as saturated polyester or polycaprolactone. It was confirmed that an excellent resin composition that can further enhance the low shrinkage effect and exhibit a remarkable synergistic effect can be obtained.
(実施例2)
(1) (A)成分として水添ビスフェノール・Aお
よびネオペンチルグリコールを含む二重結合当りの分子
量約220の不飽和ポリエステル樹脂65重量部を、ハ
イドロキノン0,01重量部を溶解したの)成分として
のスチレンモノマー(日本ユビヵ(株)製〕85重量部
に溶解した溶液を作った(この溶液をrUP−2Jと称
する)。(Example 2) (1) 65 parts by weight of an unsaturated polyester resin containing hydrogenated bisphenol A and neopentyl glycol as components (A) and having a molecular weight of approximately 220 per double bond is dissolved in 0.01 part by weight of hydroquinone. A solution was prepared by dissolving 85 parts by weight of styrene monomer (manufactured by Nippon Yubika Co., Ltd.) as a component (this solution was referred to as rUP-2J).
(2)(ト)成分としてマレイン酸およびプロピレング
リコールから・なる不飽和ポリエステル樹脂65重量部
を上記と同様のスチレンモノマー85重量部に溶解した
溶液を作った(この溶液をrUP −8」と称する)。(2) A solution was prepared by dissolving 65 parts by weight of an unsaturated polyester resin consisting of maleic acid and propylene glycol as component (g) in 85 parts by weight of the same styrene monomer as above (this solution is referred to as rUP-8). ).
(8)(ト))成分としてポリスチレン主鎖にポリカプ
ロラクトンをグラフ。ト重合させた共重合体(分子を約
20.000 ) 80重量部を上記と同様のスチレン
モノマー70重量部に溶解した溶液を作った(この溶液
をrM−IJと称する)。(8) Graph of polycaprolactone on the polystyrene main chain as the component (g). A solution was prepared by dissolving 80 parts by weight of the polymerized copolymer (approximately 20,000 molecules) in 70 parts by weight of the same styrene monomer as above (this solution was referred to as rM-IJ).
(4)実施例1におけると同様にして「UP−IJ。(4) “UP-IJ” in the same manner as in Example 1.
rsBs −IJおよび「PCI、−IJを作った。rsBs -IJ and "PCI, -IJ were made.
生成した各溶液を表4に示す配合量で配合して本発明の
樹脂組成物を調製する試験、%lV、 Vお工び■を行
った。Tests were conducted in which the resin compositions of the present invention were prepared by blending each of the produced solutions in the amounts shown in Table 4.
表 4
上述するようにし7て調製した各樹脂組成物をそれぞれ
約2mFの試験管に入れ、室温(約20℃)で放置し、
7日後に各樹脂組成物の相分離状態を調べた。、また、
比較の目的のためKM−1を含まない組成物として実施
例1の表1に示す試験/i61および■の樹脂組成物に
ついて同様にして相分離状態を調べた。これらの結果を
表5に示す。Table 4 Each resin composition prepared as described above was placed in a test tube of about 2 mF, left at room temperature (about 20°C),
Seven days later, the state of phase separation of each resin composition was examined. ,Also,
For the purpose of comparison, the state of phase separation was similarly investigated for the resin compositions of Test/i61 and (2) shown in Table 1 of Example 1 as compositions not containing KM-1. These results are shown in Table 5.
表 5
(評価基準) 十 分離
+十 一部分分離
−全く分離せず相客 、
上記表5から1M−1を含まない試験AIおよび■の樹
脂組成物に比べ1M−1を含む試験AIV。Table 5 (Evaluation Criteria) Adequate Separation + Enough Partial Separation - No separation at all From Table 5 above, Test AIV containing 1M-1 compared to Test AI not containing 1M-1 and the resin composition of ■.
■および■は相分離を全く生じないか、または一部分相
分離を生ずる程度であることがわかる。特に、試験屋■
のUP−17SBS−1/POL−1/M −1の系で
は全く相分離が生ぜず、極めて均質な樹脂組成物である
ことがわかる。It can be seen that in cases (1) and (2), no phase separation occurred at all or only some phase separation occurred. In particular, the testing shop
It can be seen that in the system UP-17SBS-1/POL-1/M-1, no phase separation occurred at all, and the resin composition was extremely homogeneous.
更に1表4に示す試験AN〜■の樹脂組成物を用い、実
施例1の表2に記載すると同様にベンゾエート、ステア
リン酸亜鉛、酸化マグネシウム(たローこの酸化マグネ
シウム位増粘粘度が2〜8XIOCpSになるように配
合量を設定)、炭酸カルシウムおよびガラス繊維を配合
し、同様にしてシート化してSMOを形成した。この形
成しfcSMOを実施例1に記載すると同様に加圧成形
して、成形物を成形した。各成形物の物性について測定
した結果を表6に示す。また、比較の目的のためにM−
1を含まない成形物として実施例1の表2に示す試料A
I〜■のSM(3から作った成形物について、同様の物
性を測定し、その結果を、また表6に示す。Furthermore, using the resin compositions of Tests AN to ■ shown in Table 1, and as described in Table 2 of Example 1, benzoate, zinc stearate, and magnesium oxide (Taro's magnesium oxide viscosity increase of 2 to 8XIOCpS) were used. ), calcium carbonate and glass fiber were blended and formed into a sheet in the same manner to form an SMO. This formed fcSMO was pressure molded in the same manner as described in Example 1 to form a molded product. Table 6 shows the results of measuring the physical properties of each molded product. Also, for comparison purposes, M-
Sample A shown in Table 2 of Example 1 as a molded product not containing 1
The same physical properties were measured for the molded products made from SM (3) of I to ■, and the results are also shown in Table 6.
表6
×・・・・液状物が表面近くに点在し、フィルムが極め
てはがれにくい。Table 6 ×: Liquid substances are scattered near the surface, and the film is extremely difficult to peel off.
△・・・・液状物がわずかに認められ、フィルムがはが
しにくい。△: A slight amount of liquid was observed, and the film was difficult to peel off.
○・・・・液状物が殆んど認められないが、フィルムが
若干はがれにくい。○: Almost no liquid was observed, but the film was slightly difficult to peel off.
◎・・・・液状物が認められず、粘着性もない。◎・・・No liquid substance was observed, and there was no stickiness.
上記・表6から1本発明の組成であるI、 ■、 Vお
よび■は、いずれも収縮率がマイナス、すなわち、膨張
するのでヒケ等の太きなうねシを生ずることもなく1表
面平滑性も良いことがわかる(すなわ°ち、小孕なうね
りもなく良好な表面品位が得られることがわかる〕。From Table 6 above, compositions I, ■, V and ■ of the present invention all have a negative shrinkage rate, that is, they expand, so they do not produce thick ridges such as sink marks and have a smooth surface. It can be seen that the surface quality is also good (in other words, it can be seen that a good surface quality without small waviness can be obtained).
(発明の効果) 本発明においては、樹脂組成物を上述する(4)。(Effect of the invention) In the present invention, the resin composition is described above (4).
(B)、 (01おj二び■、成分を配合することにょ
シ、またはこれら4成分に更に■)成分を配合すること
により表面平滑性、寸法安定性、塗料接着性などに優れ
たシート状成形用材料に使用する成形用樹脂組成物を得
ることができた。(B), A sheet with excellent surface smoothness, dimensional stability, paint adhesion, etc. by blending (01), (01), or (2) components, or by further blending these four components with (■) components. A molding resin composition to be used as a shaped molding material could be obtained.
Claims (1)
ブタジエン−スチレンブロック共重合体、(C)ポリカ
プロラクトンおよび(D)共重合可能な単量体を配合し
てなることを特徴とする成形用樹脂組成物。1, (A) unsaturated polyester resin, (B) styrene-
A molding resin composition comprising a butadiene-styrene block copolymer, (C) polycaprolactone, and (D) a copolymerizable monomer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13907884A JPS6119655A (en) | 1984-07-06 | 1984-07-06 | Resin composition for molding |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13907884A JPS6119655A (en) | 1984-07-06 | 1984-07-06 | Resin composition for molding |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6119655A true JPS6119655A (en) | 1986-01-28 |
Family
ID=15236969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13907884A Pending JPS6119655A (en) | 1984-07-06 | 1984-07-06 | Resin composition for molding |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6119655A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61148265A (en) * | 1984-12-21 | 1986-07-05 | Kanegafuchi Chem Ind Co Ltd | Unsaturated polyester resin composition and laminate |
EP0234902A2 (en) * | 1986-02-22 | 1987-09-02 | Takemoto Yushi Kabushiki Kaisha | Hardenable unsaturated polyester resin compositions |
-
1984
- 1984-07-06 JP JP13907884A patent/JPS6119655A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61148265A (en) * | 1984-12-21 | 1986-07-05 | Kanegafuchi Chem Ind Co Ltd | Unsaturated polyester resin composition and laminate |
EP0234902A2 (en) * | 1986-02-22 | 1987-09-02 | Takemoto Yushi Kabushiki Kaisha | Hardenable unsaturated polyester resin compositions |
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