【発明の詳細な説明】[Detailed description of the invention]
（産業上の利用分野）
本発明は、線膨張率が小さく而も物性及び外観
が優れた成形品、特に雨樋、デツキ材、窓枠等の
薄肉成形品に好適な塩化ビニル系樹脂組成物に関
する。
（従来技術）
近年、塩化ビニル系樹脂製成形品、例えば、硬
質塩化ビニル製雨樋が多く用いられるようになつ
てきているが、硬質塩化ビニル製雨樋は金属製雨
樋と比べて線膨張率が大きく、使用時、気温の変
化により、長手方向の長さが変化して接続部又は
止め金具の部分で変形や破損を起こしたり、日射
を直接受けた部分が熱膨張して曲がつたり波打つ
たりしやすいという欠点があつた。
しかして、従来、特公昭53−21891号公報に記
載の如く、50〜180の粘度指数のビニル樹脂100重
量部と、個々の粒子の平均直径が0.05〜50μであ
る無機充填剤10〜60重量部と、潤滑剤1.5〜５重
量部と、長さ４〜６mmのガラス繊維５〜40重量部
とを有する押出成形組成物が提案されているが、
ガラス繊維が樹脂中に均一に分散しにくく、又混
入されたガラス繊維とビニル樹脂との接着性が悪
くて、ガラス繊維の周りに大きな空隙が発生し、
このためガラス繊維が加えられる前のビニル樹脂
に比べて、成形品の耐衝撃性等の物性が著しく低
下してしまい、又成形性が著しく悪くなり、成形
品の表面状態が滑らかとならず、外観が悪いばか
りでなく、これが起因して、屋外で使用された時
に短時間の内に白化する（チヨーキング）という
欠点があつた。
（発明の目的）
本発明者は、如上の事実に鑑がみ、鋭意検討し
た結果、ガラス短繊維の長さを極く短くし、且つ
ガラス短繊維と樹脂との間の密着性を良くする改
質剤を加え、更に成形時の練りを良くする加工助
剤を加え、且つ成形品の耐候性を改良する紫外線
吸収剤を加えることにより、叙上の如き従来の欠
点を解消し得ることを見い出し本発明をなすに至
つたものであり、本発明は、線膨張率が小さくて
熱変形が起こりにくく、しかも耐衝撃性等の物性
が優れ、且つ成形性及び耐候性が優れ、表面状態
の滑らかな成形品、特に雨樋、デツキ材、窓枠等
の薄肉の成形品に好適な塩化ビニル系樹脂組成物
を提供することを目的とするものである。
（発明の要旨）
本発明の要旨は、塩化ビニル系樹脂100重量部
に、ガラス短繊維５乃至30重量部と、無機充填剤
10乃至50重量部と、塩素化ポリエチレンからなる
改質剤５乃至220重量部と、ポリメチルメタアク
リレートからなる加工助剤１乃至５重量部と、紫
外線吸収剤0.05乃至0.5重量部とを加えてなる塩
化ビニル系樹脂組成物に存する。
（発明の構成）
本発明に使用される塩化ビニル系樹脂として
は、例えば、ポリ塩化ビニル（PVC）、ポリ塩化
ビニリデン及び塩素化ポリ塩化ビニル（塩素化
PVC）等が好適に使用され、就中、ポリ塩化ビ
ニル（PVC）が特に好適に使用される。
本発明に使用されるガラス短繊維としては、例
えば、ストランドが長さ0.05〜３mm（成形品中に
存在時）に切断されたガラスチヨツプや、長さ
0.05〜３mm（成形品中に存在時）に切断されたパ
イル状のもの等が好適に使用され、就中、長さ
0.05〜３mm（成形品中に存在時）に切断されたガ
ラスチヨツプが特に好適に使用され、又エポキシ
シラン等のカツプリング処理剤にて表面処理され
たものが好適に使用される。
本発明に使用される無機充填剤としては、例え
ば、沈降性炭酸カルシウム、軽微性炭酸カルシユ
ウム、極微細炭酸カルシウムの如き炭酸カルシウ
ム、シリカ、タルク、ケイソウ土、クレー、マイ
カ等のケイ酸塩及びアルミナ等が好適に使用さ
れ、就中、極微細炭酸カルシウムが特に好適に使
用され、又有機酸塩等で表面処理されたものが好
適に使用され、又粒径が0.1μ以下のものが好適に
使用される。
本発明に使用される改質剤としては、系中に加
えられることにより、ガラス短繊維と塩化ビニル
系樹脂との間の密着性を改良し、ガラス短繊維の
周りに発生する空隙を小さく押さえ、成形品の耐
衝撃強度等を向上させるもので、塩素化ポリエチ
レン（塩素化PE）が使用される。
本発明に使用される加工助剤としては、ポリメ
チルメタアクリレート（PMMA）が使用される。
本発明に使用される紫外線吸収剤としては、例
えば、サリシレートエステル、ベンゾエートエス
テル、ベンゾフエノン系、ベンゾトリアゾール系
およびアクリルニトリル系が好適に使用される。
本発明においては、上記のものの他、安定剤、
顔料が必要に応じて併用されてもよい。
本発明においては、上記のものの他、安定剤、
顔料が必要に応じて併用されてもよい。
本発明においては、他の成分と共に、ガラス短
繊維を、塩化ビニル系樹脂100重量部に対して、
５乃至30重量部加えることにより、成形性及び耐
衝撃性等を悪くさせることなく、成形品の線膨張
率を小さくし、且つ剛性を大きくし、温度変化に
より熱変形しにくくする。ガラス短繊維が全く加
えられていないか又はその添加量が塩化ビニル系
樹脂100重量部に対して、５重量部未満の少量加
えられただけでは、充分な効果が期待できず、又
30重量部を越えるような多量加えられた場合は、
成形性が悪くなり、成形品の外観が滑らかと成ら
ず、又耐衝撃性及び耐候性が悪くなつてしまう。
本発明においては、他の成分と共に、無機充填
剤を、塩化ビニル系樹脂100重量部に対して、10
乃至50重量部加えることにより、耐候性及び耐衝
撃性等を悪くさせることなく、成形品の、剛性を
改良し、温度変化により熱変形しにくくする。無
機充填剤が全く加えられないか又はその添加量が
塩化ビニル系樹脂100重量部に対して10重量部未
満の少量加えられただけでは、充分な効果が期待
できず、又50重量部を越えるような多量加えられ
た場合は、耐衝撃性及び耐候性が悪くなつてしま
う。
本発明においては、他の成分と共に、前記改質
剤を、塩化ビニル系樹脂100重量部に対して、５
乃至20重量部加えることにより、線膨張率を大き
くさせることなく、成形品の耐衝撃性及び剛性等
の物性を改良する。改質剤が全く加えられないか
又は５重量部未満の少量加えられただけでは、充
分な効果が期待できず、又20重量部を越えるよう
な多量加えられた場合は、線膨張率が大きくなつ
てしまう。
本発明においては、他の成分と共に、前記加工
助剤を、塩化ビニル系樹脂100重量部に対して、
１乃至10重量部加えることにより、線膨張率を大
きくさせることなく、改質剤と共に、成形品の耐
衝撃性及び剛性等の物性を一層改良する。加工助
剤が全く加えられないか又は１重量部未満の少量
加えられただけでは充分な効果が期待できず、又
５重量部を越えるような多量加えられた場合は、
成形品の線膨張率が大きくなつてしまう。
本発明においては、他の成分と共に、紫外線吸
収剤を、塩化ビニル系樹脂100重量部に対して、
0.05乃至0.5重量部加えることにより、成形品の
使用時における昇温を防止し、耐候性を改良す
る。紫外線吸収剤が全く加えられないか又は0.05
重量部末満の少量加えられるだけでは充分な効果
が期待できず、又0.5重量部を越えるような多量
加えても、有効に耐候性改良に寄与しない。
（発明の効果）
本発明塩化ビニル系樹脂組成物は、塩化ビニル
系樹脂100重量部に、ガラス短繊維５乃至30重量
部と、無機充填剤10乃至50重量部と、前記改質剤
５乃至20重量部と、前記加工助剤１乃至５重量部
と、紫外線吸収剤0.05乃至0.5重量部とを加えて
なるものであるので、成形品の、線膨張率が小さ
くて温度変化による熱変形が起こりにくく、而も
抗張力、耐衝撃性の物性が優れており、且つ成形
性が極めて良く、成形品の表面状態が滑らかであ
り、外観がよく、又これと紫外線吸収剤を入れた
ことにより、成形品の使用時における昇温を防止
し、耐候性が著しく改良され、屋外で使用した時
に短時間の内に白化する（チヨーキング）ことが
ない。
以下本発明を実施例により説明する。
（実施例 １，２）
第１表に示す配合物（ガラス短繊維は、長さ２
〜５mm、径約13μで、表面がエポキシシランで処
理されたもの使用）を混合機にて120℃で６分間
加熱混合し、この混合物をロール混練機にて160
℃で５分間混練して厚さ1.2mmのシート状物を作
り、このシート状物を粉砕して３mm角の粉砕片を
作り、この粉砕片を押出機、金型にて樹脂温度
180乃至185℃で押出して、厚さ1.2mmの薄肉異形
成形品を押出成形した。
成形品より試験片を切り出して、線膨張率、抗
張力、伸び、衝撃強度、熱収縮率、耐候性及び成
形品中のガラス短繊維の長さを測定し、又成形品
中のガラス短繊維と樹脂との間の密着性を観察し
た。その結果を実施例１，２として第１表に示
す。
（比較例 １）
第１表の比較例１の配合物を混合機にて良く混
合し、この混合物を押出機、金型にて樹脂温度
180乃至185℃で押出して、厚さ1.2mmの薄肉異形
成形品を押出成形した。その成形品より試験片を
切り出して、線膨張率、抗張力、伸び、熱収縮率
及び耐候性を測定した結果を比較例１として第１
表に併せて示す。
（比較例 ２）
第１表の比較例２の配合物（ガラス短繊維は、
長さ４〜６mmで、表面エポキシシランで処理され
たもの使用）を比較例１と同様の成形を試みた
が、成形性が悪く成形ができなかつたので、第２
表に示す配合物を混合機にて常温で混合し、この
混合物をロール混練機にて190℃で５分間混練し
て厚さ1.2mmのシート状物を作り、このシート状
物を切り出して、ハンドプレスにて、190℃50
Kg／cm2で２分間予熱後、190℃100Kg／cm2で１分間
プレスして1.3mmのシートを作製し、このシート
より試験片を切り出して実施例と同様の測定及び
観察を行つた結果を比較例２として第１表に併せ
て示す。
尚、線膨張率については、ASTM：D696にて
測定した。抗張力及び伸びについては、
JISA5706にて測定した。衝撃強度については、
JISA5400にて測定した。熱収縮率については、
成形品よりその長手方向に長さ200mmの試験片を
切り出し３箇所に100mm間隔に線を入れ、この試
験片をギアーオーブンにて100℃15分間加熱後取
り出し室温に放置した後、線間の長さを測定し
て、もとの長さに対する収縮の度合（％）を算出
した。又耐候性については、JISA1415の条件よ
りも圧力4.5〜５Kgｆ／cm2に上げた促進条件にて
測定した。又成形品中のガラス短繊維と樹脂との
間の密着性は、試験片の断面を電子顕微鏡にて見
てガラス短繊維の周りの空隙の発生状態を観察す
ることにより判断した。
第１表からも明らかな如く、実施例１，２の場
合はいずれも、線膨張率が小さく、而も耐衝撃性
等の物性がガラス短繊維が分散されていない比較
例１の値に匹敵する程向上しており、又成形性は
1.2mmの薄肉成形品の成形が可能であり、成形品
の表面状態も滑らかで均一であり極めて良好であ
つた。又ガラス短繊維の周りには部分的に僅かに
極く小さい空隙が見られる程度で、ガラス短繊維
と樹脂との間が良く密着している様子が観察され
た。又耐候性もガラス短繊維が分散されていない
比較例１の値に匹敵する程向上しており、著しく
良かつた。
尚、第１表からも明らかな如く、比較例１の場
合は線膨張率が著しく大きく温度変化により変形
しやすいものである。又比較例２の場合は、成形
性が悪く、薄肉異形成形品の成形ができず、又耐
衝撃性等の物性及び耐候性がとても実用に供する
ことができない程悪かつた。又ガラス短繊維の周
りには大きい空隙が見られ、ガラス短繊維と樹脂
との間は密着していなかつた。
(Industrial Application Field) The present invention is a vinyl chloride resin composition suitable for molded products having a small coefficient of linear expansion and excellent physical properties and appearance, especially thin-walled molded products such as rain gutters, decking materials, and window frames. Regarding. (Prior art) In recent years, molded products made of vinyl chloride resin, such as rain gutters made of hard vinyl chloride, have come into widespread use. During use, the longitudinal length may change due to changes in temperature, causing deformation or damage at the connection or fasteners, or parts directly exposed to sunlight may expand and bend. The drawback was that it was prone to rippling. Conventionally, as described in Japanese Patent Publication No. 53-21891, 100 parts by weight of a vinyl resin having a viscosity index of 50 to 180 and 10 to 60 parts by weight of an inorganic filler whose individual particles have an average diameter of 0.05 to 50μ have been used. extrusion compositions have been proposed having 1.5 to 5 parts by weight of lubricant and 5 to 40 parts by weight of glass fibers having a length of 4 to 6 mm.
It is difficult for the glass fibers to be uniformly dispersed in the resin, and the adhesion between the mixed glass fibers and the vinyl resin is poor, resulting in large voids around the glass fibers.
As a result, compared to the vinyl resin before glass fibers are added, the physical properties of the molded product such as impact resistance are significantly reduced, and the moldability is also significantly deteriorated, resulting in the surface condition of the molded product not being smooth. Not only does it have a poor appearance, but this also has the disadvantage of whitening within a short period of time when used outdoors. (Purpose of the Invention) In view of the above facts and as a result of intensive study, the present inventor has made the length of the short glass fibers extremely short and improved the adhesion between the short glass fibers and the resin. By adding a modifier, a processing aid that improves kneading during molding, and an ultraviolet absorber that improves the weather resistance of the molded product, we believe that the above-mentioned conventional drawbacks can be overcome. The present invention has a low coefficient of linear expansion, is resistant to thermal deformation, has excellent physical properties such as impact resistance, has excellent moldability and weather resistance, and has a surface condition that is The object of the present invention is to provide a vinyl chloride resin composition suitable for smooth molded products, particularly thin molded products such as rain gutters, decking materials, and window frames. (Summary of the Invention) The gist of the present invention is to add 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, and an inorganic filler.
10 to 50 parts by weight, 5 to 220 parts by weight of a modifier made of chlorinated polyethylene, 1 to 5 parts by weight of a processing aid made of polymethyl methacrylate, and 0.05 to 0.5 parts by weight of an ultraviolet absorber. It consists of a vinyl chloride resin composition. (Structure of the Invention) Examples of the vinyl chloride resin used in the present invention include polyvinyl chloride (PVC), polyvinylidene chloride, and chlorinated polyvinyl chloride (chlorinated polyvinyl chloride).
PVC), among others, polyvinyl chloride (PVC) is particularly preferably used. Examples of short glass fibers used in the present invention include glass chops whose strands are cut into lengths of 0.05 to 3 mm (when present in a molded product), and
Pile-shaped materials cut into 0.05 to 3 mm (when present in the molded product) are preferably used;
Glass chips cut to 0.05 to 3 mm (when present in the molded product) are particularly preferably used, and those whose surface has been treated with a coupling treatment agent such as epoxy silane are also preferably used. Inorganic fillers used in the present invention include, for example, calcium carbonate such as precipitated calcium carbonate, light calcium carbonate, ultrafine calcium carbonate, silica, talc, diatomaceous earth, clay, mica, and other silicates, and alumina. Among these, ultrafine calcium carbonate is particularly preferably used, and those surface-treated with organic acid salts are preferably used, and those with a particle size of 0.1μ or less are preferably used. used. The modifier used in the present invention is added to the system to improve the adhesion between the short glass fibers and the vinyl chloride resin, and to reduce the voids that occur around the short glass fibers. , chlorinated polyethylene (chlorinated PE) is used to improve the impact resistance and strength of molded products. The processing aid used in the present invention is polymethyl methacrylate (PMMA). As the ultraviolet absorbent used in the present invention, for example, salicylate ester, benzoate ester, benzophenone type, benzotriazole type and acrylonitrile type are suitably used. In the present invention, in addition to the above, stabilizers,
Pigments may be used in combination as necessary. In the present invention, in addition to the above, stabilizers,
Pigments may be used in combination as necessary. In the present invention, along with other components, short glass fibers are added to 100 parts by weight of vinyl chloride resin.
By adding 5 to 30 parts by weight, the coefficient of linear expansion of the molded product is reduced, the rigidity is increased, and the molded product is resistant to thermal deformation due to temperature changes without deteriorating moldability, impact resistance, etc. If short glass fibers are not added at all or if only a small amount of less than 5 parts by weight is added to 100 parts by weight of vinyl chloride resin, sufficient effects cannot be expected.
If a large amount exceeding 30 parts by weight is added,
The moldability deteriorates, the appearance of the molded product is not smooth, and the impact resistance and weather resistance deteriorate. In the present invention, 10 parts by weight of an inorganic filler is added to 100 parts by weight of vinyl chloride resin along with other components.
By adding 50 to 50 parts by weight, the rigidity of the molded product is improved and it becomes less susceptible to thermal deformation due to temperature changes without deteriorating weather resistance, impact resistance, etc. If an inorganic filler is not added at all or if it is added in a small amount of less than 10 parts by weight per 100 parts by weight of vinyl chloride resin, a sufficient effect cannot be expected, or if it is added in an amount exceeding 50 parts by weight. If such a large amount is added, impact resistance and weather resistance will deteriorate. In the present invention, 5 parts by weight of the modifier and other components are added to 100 parts by weight of the vinyl chloride resin.
By adding 20 to 20 parts by weight, physical properties such as impact resistance and rigidity of the molded product can be improved without increasing the coefficient of linear expansion. If the modifier is not added at all or if it is added in a small amount (less than 5 parts by weight), a sufficient effect cannot be expected, and if it is added in a large amount (over 20 parts by weight), the coefficient of linear expansion will be large. I get used to it. In the present invention, along with other components, the processing aid is added to 100 parts by weight of the vinyl chloride resin.
By adding 1 to 10 parts by weight, together with the modifier, the physical properties such as impact resistance and rigidity of the molded article are further improved without increasing the coefficient of linear expansion. If the processing aid is not added at all or if it is added in a small amount of less than 1 part by weight, a sufficient effect cannot be expected, and if it is added in a large amount exceeding 5 parts by weight,
The coefficient of linear expansion of the molded product becomes large. In the present invention, along with other components, a UV absorber is added to 100 parts by weight of vinyl chloride resin.
By adding 0.05 to 0.5 parts by weight, temperature rise during use of the molded product is prevented and weather resistance is improved. No UV absorber added or 0.05
If only a small amount of less than 0.5 parts by weight is added, a sufficient effect cannot be expected, and even if added in a large amount exceeding 0.5 parts by weight, it will not contribute effectively to improving weather resistance. (Effects of the Invention) The vinyl chloride resin composition of the present invention contains 100 parts by weight of vinyl chloride resin, 5 to 30 parts by weight of short glass fibers, 10 to 50 parts by weight of an inorganic filler, and 5 to 5 parts by weight of the above-mentioned modifier. 20 parts by weight, 1 to 5 parts by weight of the processing aid, and 0.05 to 0.5 part by weight of the ultraviolet absorber, so the linear expansion coefficient of the molded product is small and thermal deformation due to temperature changes is low. It has excellent physical properties such as tensile strength and impact resistance, has very good moldability, has a smooth surface, and has a good appearance. It prevents temperature rise during use of molded products, significantly improves weather resistance, and prevents whitening (chyoking) within a short period of time when used outdoors. The present invention will be explained below with reference to Examples. (Examples 1 and 2) The formulations shown in Table 1 (short glass fibers had a length of 2
5mm in diameter, approximately 13μ in diameter, and whose surface was treated with epoxy silane) were heated and mixed in a mixer at 120°C for 6 minutes, and this mixture was mixed in a roll kneader at 160°C.
Knead for 5 minutes at ℃ to make a sheet with a thickness of 1.2 mm, crush this sheet to make 3 mm square crushed pieces, and use an extruder and mold to heat the crushed pieces to resin temperature.
Extrusion was carried out at 180 to 185°C to extrude a thin profiled article with a thickness of 1.2 mm. A test piece was cut out from the molded product, and the coefficient of linear expansion, tensile strength, elongation, impact strength, heat shrinkage rate, weather resistance, and length of the short glass fibers in the molded product were measured. The adhesion with the resin was observed. The results are shown in Table 1 as Examples 1 and 2. (Comparative Example 1) The formulation of Comparative Example 1 in Table 1 was mixed well in a mixer, and the mixture was heated in an extruder and a mold to adjust the resin temperature.
Extrusion was carried out at 180 to 185°C to extrude a thin profiled article with a thickness of 1.2 mm. A test piece was cut out from the molded product, and the linear expansion coefficient, tensile strength, elongation, heat shrinkage rate, and weather resistance were measured.
It is also shown in the table. (Comparative Example 2) The formulation of Comparative Example 2 in Table 1 (short glass fibers were
I tried to mold the same material as in Comparative Example 1, but the moldability was poor and I could not mold it.
The formulations shown in the table are mixed in a mixer at room temperature, this mixture is kneaded in a roll kneader at 190°C for 5 minutes to make a sheet with a thickness of 1.2 mm, and this sheet is cut out. Hand press at 190℃50
After preheating at Kg/cm 2 for 2 minutes, a 1.3 mm sheet was prepared by pressing at 190°C and 100 Kg/cm 2 for 1 minute, and test pieces were cut from this sheet and subjected to the same measurements and observations as in the examples. is also shown in Table 1 as Comparative Example 2. The coefficient of linear expansion was measured using ASTM: D696. Regarding tensile strength and elongation,
Measured according to JISA5706. Regarding impact strength,
Measured using JISA5400. Regarding heat shrinkage rate,
Cut out a test piece with a length of 200 mm in the longitudinal direction from the molded product, insert lines at 100 mm intervals in three places, heat this test piece in a gear oven at 100°C for 15 minutes, take it out, leave it at room temperature, and measure the length between the lines. The length was measured and the degree of shrinkage (%) relative to the original length was calculated. Weather resistance was measured under accelerated conditions with a pressure of 4.5 to 5 Kgf/cm 2 higher than the JISA1415 conditions. The adhesion between the short glass fibers and the resin in the molded article was determined by viewing the cross section of the test piece under an electron microscope and observing the generation of voids around the short glass fibers. As is clear from Table 1, in both Examples 1 and 2, the coefficient of linear expansion is small, and the physical properties such as impact resistance are comparable to those of Comparative Example 1 in which short glass fibers are not dispersed. It has improved as much as possible, and the moldability has improved as well.
It was possible to mold a 1.2 mm thin-walled molded product, and the surface condition of the molded product was smooth and uniform, which was extremely good. In addition, it was observed that the short glass fibers and the resin were in close contact with each other, with only very small voids partially visible around the short glass fibers. Furthermore, the weather resistance was improved to the extent that it was comparable to that of Comparative Example 1 in which short glass fibers were not dispersed, and was extremely good. As is clear from Table 1, Comparative Example 1 has a significantly large coefficient of linear expansion and is easily deformed due to temperature changes. In the case of Comparative Example 2, the moldability was poor, making it impossible to mold a thin irregular shaped article, and the physical properties such as impact resistance and weather resistance were so poor that they could not be put to practical use. Also, large voids were observed around the short glass fibers, and the short glass fibers and the resin were not in close contact.
【表】
◎；薄肉異形成形品の形状に成形でき、又成形品の
表面状態は滑らかで均一であつた。
×；薄肉異形成形品の形状に成形できなかつた。
[Table] ◎: It was possible to mold into the shape of a thin-walled irregularly shaped article, and the surface condition of the molded article was smooth and uniform.
×: It was not possible to mold the product into the shape of a thin-walled irregularly shaped article.