JPS6021707B2 - Vinyl chloride resin composition with excellent weather resistance - Google Patents
Vinyl chloride resin composition with excellent weather resistanceInfo
- Publication number
- JPS6021707B2 JPS6021707B2 JP16640179A JP16640179A JPS6021707B2 JP S6021707 B2 JPS6021707 B2 JP S6021707B2 JP 16640179 A JP16640179 A JP 16640179A JP 16640179 A JP16640179 A JP 16640179A JP S6021707 B2 JPS6021707 B2 JP S6021707B2
- Authority
- JP
- Japan
- Prior art keywords
- chloride resin
- vinyl chloride
- calcium carbonate
- weather resistance
- 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
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
本発明は塩化ビニル樹脂組成物に係るもので詳しくは塩
化ビニル樹脂に充填剤として表面改質炭酸カルシウムを
添加した耐候性の優れた塩化ビニル樹脂組成物に関るも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a vinyl chloride resin composition, and more particularly, to a vinyl chloride resin composition with excellent weather resistance in which surface-modified calcium carbonate is added as a filler to vinyl chloride resin. It is.
現在、塩化ビニル樹脂製品には雨樋、デッキ製品、ベン
チなど屋外の日光暴露下に使用されるものが多くなって
きているが、この様な屋外または紫外線暴露下における
塩化ピニル樹脂製品（以下塩ビ製品）の寿命は、他のプ
ラスチック製品と同様、先ず初期段階では劣化による外
観的な表面白化が表われ、それから逐次劣化が内部に進
行し、最後は崩壊、使用に耐えられなくなる。Currently, many PVC resin products are used outdoors under sunlight exposure, such as rain gutters, deck products, and benches. As with other plastic products, the product's lifespan begins with external whitening due to deterioration in the initial stage, then deterioration progresses internally, and eventually it collapses and becomes unusable.
そこで耐腰性の優れた塩ビ製品としては、先ず屋外また
は紫外線暴露で外観的に表面白化の発生しないもの、あ
るいは発生の出来る限り遅いものが極力要望されている
。一方、塩ビ製品については剛性、寸法安定性、耐熱性
、難燃性などの向上、燃焼時に発生する塩酸ガスの捕捉
、その他の目的で、炭酸カルシウム充填剤の添加される
ことはすでに公知である。Therefore, as a PVC product with excellent stiffness resistance, there is a strong demand for one that does not cause surface whitening when exposed outdoors or to ultraviolet rays, or one that does so as slowly as possible. On the other hand, it is already known that calcium carbonate filler is added to PVC products to improve rigidity, dimensional stability, heat resistance, flame retardance, etc., to capture hydrochloric acid gas generated during combustion, and for other purposes. .
塩ビ製品に炭酸カルシウムを添加、応用すると数々のメ
リットも得られるが、また同時にデメリットも生じてく
る。そのデメリットの一つに炭酸カルシウムを添加した
塩ビ製品を屋外暴露すると耐候性の低下することが挙げ
られる。すなわち塩化ビニル樹脂は炭酸カルシウムを添
加すると、添加しない場合に比べて、室外暴路による劣
化とくに白化劣化が促進される。なお、このような塩化
ビニル樹脂の充填剤配合による白イＧ劣化は、炭酸カル
シウムばかりでなく、耐酸性の優れたクレー、石英粉な
どの充填剤でも認められる一般的な現象である。本発明
者等は塩化ビニル樹脂に添加、応用しても屋外または紫
外線暴露下でも耐候性の低下しない炭酸カルシウムにつ
いて、鋭意研究した結果、驚くべきことに適当な処理剤
で表面教質した炭酸カルシウムが塩ビ製品の耐候性を低
下させないばかりか、むしろ向上させることを発見し、
本発明を完成するに到った。Adding and applying calcium carbonate to PVC products brings many benefits, but at the same time there are also disadvantages. One of the disadvantages is that when PVC products containing calcium carbonate are exposed outdoors, their weather resistance decreases. That is, when calcium carbonate is added to vinyl chloride resin, deterioration due to outdoor rough roads, especially whitening deterioration, is accelerated compared to when calcium carbonate is not added. Incidentally, such white G deterioration due to filler blending of vinyl chloride resin is a general phenomenon observed not only with calcium carbonate but also with fillers such as clay and quartz powder, which have excellent acid resistance. As a result of extensive research into calcium carbonate, which does not reduce weather resistance even when added to vinyl chloride resin and applied outdoors or under exposure to ultraviolet rays, the inventors of the present invention found that calcium carbonate whose surface had been treated with an appropriate treatment agent was surprisingly found. discovered that not only does it not reduce the weather resistance of PVC products, but it actually improves it.
The present invention has now been completed.
すなわち、本発明は塩化ビニル樹脂に対して縞合りん酸
で表面改質した炭酸カルシウムを添加しこれらを適当に
加熱、混練して、耐候性に優れた塩化ビニル樹脂組成物
を提供するものである。That is, the present invention provides a vinyl chloride resin composition with excellent weather resistance by adding calcium carbonate whose surface has been modified with striped phosphoric acid to vinyl chloride resin, and then appropriately heating and kneading the mixture. be.
本発明における、塩化ピニル樹脂としては塩化ビニル６
０％（重量）以上の重合物、共重合物などが使用できる
。また縮合りん酸で表面敬質した炭酸カルシウムとして
は、例えば特開昭５４−３斑９７または特開昭５４−３
７０９９などで開示される方法によって造られるものを
用いればよい。すなわち、水に懸濁した炭酸カルシウム
または鷹浮流動下の炭酸カルシウム粉末にピロリン酸、
メタリン酸、その他ポリりん酸またはそれらのアルカリ
金属塩の何れか一つまたは二つ以上の縮合りん酸または
／及びその塩をＣａＣｏ３／Ｐ２Ｑ＝１００／１〜１０
０／４の重量比の範囲で添加、鷹拝することによって表
面改質炭酸カルシウムを造ることができる。塩化ビニル
樹脂１０の重量部に対する表面改質炭酸カルシウムの添
加割合は１〜１５０重量部、好ましくは１０〜１０の重
量部で、１重部以下では耐涙性の優れた塩化ビニル樹脂
組成物は得られず、また１５の重量部以上多量に添加す
ると強度が低下し、白化劣化も劣る。本発明組成物が何
故屋外暴露で耐膜性の優れた樹脂組成物を形成するか、
その理由についてまだつまびらかでないが、本発明組成
物は多分、塩化ビニル樹脂の光による劣化と樹脂組成物
内部から低分子量化合物の暴露表面へのブルーミングと
の両方の白化劣化要因がいずれも抑制され得る組成物と
なっている為と思われる。In the present invention, the pinyl chloride resin is vinyl chloride 6
0% (weight) or more of polymers, copolymers, etc. can be used. In addition, examples of calcium carbonate surface-refined with condensed phosphoric acid include JP-A-54-3 Maki 97 or JP-A-54-3
7099 or the like may be used. That is, pyrophosphoric acid is added to calcium carbonate suspended in water or calcium carbonate powder under floating flow.
Metaphosphoric acid, other polyphosphoric acids, or any one or more of their alkali metal salts, condensed phosphoric acids or/and salts thereof, CaCo3/P2Q=100/1 to 10
Surface-modified calcium carbonate can be produced by adding and mixing in a weight ratio of 0/4. The addition ratio of the surface-modified calcium carbonate to 10 parts by weight of the vinyl chloride resin is 1 to 150 parts by weight, preferably 10 to 10 parts by weight, and if it is less than 1 part by weight, the vinyl chloride resin composition with excellent tear resistance is However, if it is added in a large amount of 15 parts by weight or more, the strength decreases and the whitening deterioration is also inferior. Why does the composition of the present invention form a resin composition with excellent film resistance when exposed outdoors?
Although the reason for this is not yet clear, the composition of the present invention may be able to suppress both of the causes of whitening deterioration, namely the photo-induced deterioration of the vinyl chloride resin and the blooming of low molecular weight compounds from inside the resin composition to the exposed surface. This is probably due to the composition.
本発明組成物は、加工に際し塩化ビニル樹脂用として一
般市販の熱安定剤、光安定剤、糟剤、可塑剤、顔料、充
填剤などを加えても、本発明組成物の特徴を阻害するも
のではなく、熱安定剤、滑剤などはむしろ本発明組成物
の加工に際し添加されることが望ましい。The composition of the present invention does not inhibit the characteristics of the composition of the present invention even if generally commercially available heat stabilizers, light stabilizers, thickeners, plasticizers, pigments, fillers, etc. for vinyl chloride resin are added during processing. Rather, heat stabilizers, lubricants, etc. are preferably added during processing of the composition of the present invention.
次に本発明の実施例によってさらに詳細に説明する。Next, the present invention will be explained in more detail using examples.
実施例 １
市販の軽微性炭酸カルシウム（商品名シルバーＷ）の１
７％水懸濁液３．５ｋ９に８％ピロりん酸４４６夕を添
加、燈拝し、脱水、乾燥、粉砕してピロりん酸で表面改
質した炭酸カルシウム凶４５０夕を得た。Example 1 Commercially available minor calcium carbonate (trade name Silver W) 1
8% pyrophosphoric acid 446 was added to 7% aqueous suspension 3.5k9, dried, dehydrated, dried and ground to obtain calcium carbonate 450 which had been surface-modified with pyrophosphoric acid.
市販の塩化ビニル樹脂（重合度１０５ｕストレートポリ
マー）３００夕とピロりん酸で表面改質した炭酸カルシ
ウム凶４５夕とさらにカルシウム亜鉛系複合安定剤９夕
、ベンガラ０．６夕を混ぜて１７０ｑｏ加熱ロールで混
練し、ついで１６尊０でプレス成形して１００×１５０
×２脚厚の炭酸カルシウム■含有塩化ビニル樹脂成形板
（Ｋ）を得た。Mix 300 parts of commercially available vinyl chloride resin (straight polymer with a degree of polymerization of 105 u), 45 parts of calcium carbonate surface-modified with pyrophosphoric acid, 9 parts of a calcium-zinc composite stabilizer, and 0.6 parts of red red iron, and mix with a 170 qo heating roll. Knead it with
A calcium carbonate-containing vinyl chloride resin molded plate (K) having a thickness of ×2 was obtained.
塩化ビニル樹脂成形板（Ｋ）の屋外暴露試験結果は表１
に示し、このものは耐候性に優れていることがわかる。
実施例 ２実施例１において、ピロりん酸の代りに〆タ
りん酸を用いた以外は同様にして、メタりん酸で表面改
質した炭酸カルシウム脚、さらに炭酸カルシウム‘Ｂ｝
含有塩化ピニル樹脂成形板（Ｌ）を得た。Table 1 shows the outdoor exposure test results of vinyl chloride resin molded plate (K).
It can be seen that this material has excellent weather resistance.
Example 2 In the same manner as in Example 1, except that metaphosphoric acid was used instead of pyrophosphoric acid, calcium carbonate legs surface-modified with metaphosphoric acid, and further calcium carbonate 'B}
A molded plate (L) containing pinyl chloride resin was obtained.
塩化ビニル樹脂成形板（Ｌ）の屋外暴露試験結果は表１
に示し、このものは耐候性に優れていることがわかる。
実施例 ３
市販の塩化ビニル樹脂（重合度７００，ＶＡＣ５％のコ
ポリマ−）３００２と実施例１の炭酸カルシウム凶１８
０夕とさらに三塩基性硫酸鉛９夕、ステアリン酸鉛３夕
、ベンガラ０．６９を混ぜて１６５℃加熱ロールで混練
し、ついで１６５℃でプレス成形して１００×１５０×
２側厚の炭酸カルシウム糾合有塩化ビニル樹脂成形板（
Ｍ）を得た。Table 1 shows the outdoor exposure test results for vinyl chloride resin molded plate (L).
It can be seen that this material has excellent weather resistance.
Example 3 Commercially available vinyl chloride resin (copolymer with degree of polymerization 700, VAC 5%) 3002 and calcium carbonate 18 of Example 1
Further, 9 parts of tribasic lead sulfate, 3 parts of lead stearate, and 0.69 parts of red iron were mixed and kneaded with a heated roll at 165°C, and then press-formed at 165°C to form a 100 x 150 x
Two-sided thick calcium carbonate bonded vinyl chloride resin molded plate (
M) was obtained.
塩化ビニル樹脂成形板（Ｍ）の屋外暴露試験結果は表１
に示し、このものは耐懐性の優れていることがわかる。
比較例 １実施例１において、塩化ビニル樹脂に添加、
鶴練するピロりん酸で表面改質した炭酸カルシウム■の
代りに市販の軽微性炭酸カルシウム（商品名シルバーＷ
）あるいは車質炭酸カルシウム（商品名ホワィトンＰ−
３０）あるいはコロイド質炭酸カルシウム（商品名白艶
華ＣＣＲ）をそれぞれ層換え、その他は同様にしてそれ
ぞれの炭酸カルシウム含有塩化ビニル樹脂成形板（Ｎ）
，（０），（Ｐ）を得、それらの屋外暴露試験結果を表
１に示した。Table 1 shows the outdoor exposure test results of vinyl chloride resin molded plate (M).
It can be seen that this material has excellent resistance to erosion.
Comparative Example 1 In Example 1, added to vinyl chloride resin,
Instead of calcium carbonate surface-modified with pyrophosphoric acid, commercially available mild calcium carbonate (product name Silver W)
) or car quality calcium carbonate (trade name: Whiten P-
30) Or, change the layers of colloidal calcium carbonate (trade name: Hakuenka CCR), and do the same except for the respective calcium carbonate-containing vinyl chloride resin molded plates (N).
, (0), and (P) were obtained, and their outdoor exposure test results are shown in Table 1.
比較例 ２
実施例３において炭酸カルシウム脚の代りに軽微性炭酸
カルシウム（商品名シルバーＷ）、クレー（商品名ピグ
メン＃３０クレー）、石英粉をそれぞれ置き換え配合し
て、その他は同様にして充填剤含有塩化ビニル樹脂成形
板（Ｑ），（Ｒ），（Ｓ）を得、これらの屋外暴露試験
結果を表１に示した。Comparative Example 2 In Example 3, minor calcium carbonate (product name Silver W), clay (product name Pigmen #30 Clay), and quartz powder were substituted and blended in place of the calcium carbonate legs, and other fillers were added in the same manner. Containing vinyl chloride resin molded plates (Q), (R), and (S) were obtained, and their outdoor exposure test results are shown in Table 1.
比較例 ３
実施例１および２によって、それぞれ炭酸カルシウムを
添加せずに、その他は同様にして無充填剤塩化ピニル樹
脂成形板（Ｔ）および（Ｕ）を得、これらの屋外暴露試
験結果を表１に示した。Comparative Example 3 Non-filler pinyl chloride resin molded plates (T) and (U) were obtained according to Examples 1 and 2, without adding calcium carbonate, but in the same manner as above, and the outdoor exposure test results are shown. Shown in 1.
※ 屋外暴露の条件尼司崎市、南面、４５ｑｏ煩斜角、
一年間白化度合
◎ほとんど白化なし
○僅かに白化する
×白化する
××甚だしく白化する* Outdoor exposure conditions: Amishizaki City, south side, 45qo Fusshakaku,
Degree of bleaching for one year ◎ Almost no bleaching ○ Slight whitening × Whitening × × Severe whitening
Claims (1)
ん酸で表面改質した炭酸カルシウム１〜１５０重量部を
含むことを特徴とする耐候性の優れた塩化ビニル樹脂組
成物。1. A vinyl chloride resin composition with excellent weather resistance, characterized in that it contains 1 to 150 parts by weight of calcium carbonate surface-modified with condensed phosphoric acid as a filler in 100 parts by weight of vinyl chloride resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16640179A JPS6021707B2 (en) | 1979-12-20 | 1979-12-20 | Vinyl chloride resin composition with excellent weather resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16640179A JPS6021707B2 (en) | 1979-12-20 | 1979-12-20 | Vinyl chloride resin composition with excellent weather resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5688450A JPS5688450A (en) | 1981-07-17 |
| JPS6021707B2 true JPS6021707B2 (en) | 1985-05-29 |
Family
ID=15830726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16640179A Expired JPS6021707B2 (en) | 1979-12-20 | 1979-12-20 | Vinyl chloride resin composition with excellent weather resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6021707B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02903A (en) * | 1987-12-16 | 1990-01-05 | General Motors Corp (Gm) | Light guide method and apparatus by planar polymer |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61266450A (en) * | 1985-05-20 | 1986-11-26 | Takiron Co Ltd | Rigid vinyl chloride resin molding |
| JP5902017B2 (en) * | 2012-03-28 | 2016-04-13 | 株式会社白石中央研究所 | Surface-treated calcium carbonate and polymer composition containing the same |
-
1979
- 1979-12-20 JP JP16640179A patent/JPS6021707B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02903A (en) * | 1987-12-16 | 1990-01-05 | General Motors Corp (Gm) | Light guide method and apparatus by planar polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5688450A (en) | 1981-07-17 |
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