WO2011047521A1 - 一种树脂基复合材料洁具及其制备方法 - Google Patents

一种树脂基复合材料洁具及其制备方法 Download PDF

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Publication number
WO2011047521A1
WO2011047521A1 PCT/CN2010/000030 CN2010000030W WO2011047521A1 WO 2011047521 A1 WO2011047521 A1 WO 2011047521A1 CN 2010000030 W CN2010000030 W CN 2010000030W WO 2011047521 A1 WO2011047521 A1 WO 2011047521A1
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resin
based composite
sanitary ware
styrene
unsaturated
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PCT/CN2010/000030
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English (en)
French (fr)
Inventor
池立群
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上海琥达投资发展有限公司
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Priority to EP10706468.5A priority Critical patent/EP2347688B1/en
Priority to KR1020107003566A priority patent/KR101161552B1/ko
Priority to AU2010201219A priority patent/AU2010201219B8/en
Priority to JP2011536733A priority patent/JP5456051B2/ja
Priority to CA2698643A priority patent/CA2698643C/en
Publication of WO2011047521A1 publication Critical patent/WO2011047521A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C08G79/025—Polyphosphazenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03C—DOMESTIC PLUMBING INSTALLATIONS FOR FRESH WATER OR WASTE WATER; SINKS
    • E03C1/00—Domestic plumbing installations for fresh water or waste water; Sinks
    • E03C1/12—Plumbing installations for waste water; Basins or fountains connected thereto; Sinks
    • E03C1/18—Sinks, whether or not connected to the waste-pipe
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D11/00—Other component parts of water-closets, e.g. noise-reducing means in the flushing system, flushing pipes mounted in the bowl, seals for the bowl outlet, devices preventing overflow of the bowl contents; devices forming a water seal in the bowl after flushing, devices eliminating obstructions in the bowl outlet or preventing backflow of water and excrements from the waterpipe
    • E03D11/02—Water-closet bowls ; Bowls with a double odour seal optionally with provisions for a good siphonic action; siphons as part of the bowl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic

Definitions

  • the invention relates to a sanitary ware, in particular to a sanitary ware of a composite material mainly composed of resin and wollastonite, and a preparation method of the sanitary ware.
  • Common sanitary wares include bathtubs, washbasins, toilets, urinals and bathtubs. They are made of ceramics. Ceramics need to be fired. They are environmentally unfriendly. At the same time, many rare earth resources should be applied in the process. Rare earth mineral resources are scarce. There is bound to be some pressure on mineral resources.
  • the Chinese patent application discloses "artificial marble products and preparation method thereof" (publication number: CN1167741A), and the application is marble powder, unsaturated polyester resin, aluminum hydroxide and wollastonite.
  • the main raw material is completed by the casting process, and the product properties and preparation process are improved. Disclosure of invention
  • the technical problem to be solved by the present invention is to provide a resin-based composite sanitary ware having high toughness and high strength and low cost in view of the above-mentioned state of the art.
  • Still another technical problem to be solved by the present invention is to provide a method for preparing a resin-based composite sanitary ware which is energy-saving, environmentally friendly and low-cost.
  • a resin-based composite sanitary ware which is characterized in that the raw materials are prepared by mixing, injecting, and solidifying a mold, and the components of the raw materials and their weights are as follows:
  • the initiator is 0.8% ⁇ 2.4%.
  • the unsaturated polyester resin is prepared by diluting an unsaturated resin with styrene, wherein the weight ratio of styrene to unsaturated resin satisfies:
  • the unsaturated resin may be an o-phenyl type unsaturated polyester resin or an isophthalic type unsaturated polyester resin.
  • the polyester anti-shrinkage agent is prepared by diluting a polyester having anti-shrinking function by styrene, wherein the weight ratio of styrene and polyester satisfies:
  • the reinforcing fibers may be nylon fibers or polyphosphazene microfibers.
  • the raw material further includes a color paste having a weight ratio of 1% to 4%, and is used for preparing a bath product of various colors.
  • the raw material further includes aluminum hydroxide in a weight ratio of 6% to 10%, which can increase the texture and flame retardancy of the product.
  • the initiator comprises tert-butyl peroxybenzoate and benzoyl peroxide, and the weight ratio of tert-butyl peroxybenzoate to benzoyl peroxide is 1:2.
  • a method for preparing a resin-based composite sanitary ware comprising the steps of:
  • step 3 the mold is subjected to vacuum extraction, the degree of vacuum is -0.06 ⁇ -0.09 Pa, and the injection is performed by high pressure injection, the injection pressure is 100 kg per square centimeter, and the curing pressure after injection is 2 to 3 minutes or more. .
  • the invention has the advantages that: inexpensive wollastonite and calcium carbonate are used as main raw materials, and are prepared by high-pressure injection into a mold, so that the raw materials are easy to obtain, the cost is low, and high-energy burning is not required.
  • the consumption is reduced, the labor intensity is also reduced, the injection is made by thermosetting plastic machine, the labor efficiency is high, the product is easy to be produced on a large scale, and the defective rate is low; in addition, the obtained product has a smooth appearance as a mirror, good self-cleaning property, and the surface is non-staining, and can be maintained.
  • room temperature there is no feeling of coldness in the hand; the overall product is light, and has the advantages of high toughness and high strength. The best way to implement the invention
  • the method for preparing the Kunlun spar bathroom product mainly includes the following steps:
  • the metal injection mold of the sanitary product is heated by oil introduction, and the heating temperature is maintained at 130 ° C ⁇ 150 ° C.
  • the vacuum is extracted from the metal mold of the sanitary product, and the vacuum degree is -0.06 ⁇ - 0.09 Pascal.
  • the high-pressure composite material is injected into the metal mold, heated and solidified at high temperature for 2 minutes, which can eliminate the shrinkage deformation of the product;
  • the metal mold is opened by mechanical means, and the product is ejected from the mold by using the ejector device, and then the bathroom product is taken out from the mold by the robot and placed on the product inspection and packaging flow line.
  • the lipid fibers are also reinforcing fibers, 13% 1200 mesh wollastonite particles, 27% 1000 mesh calcium carbonate powder, 3% color paste, 1% initiator.
  • the initiator was tert-butyl oxybenzoate (TBPB) and benzoyl peroxide (BPO), and the weight ratio of tert-butyl peroxybenzoate to benzoyl peroxide was 1:2.
  • TBPB tert-butyl oxybenzoate
  • BPO benzoyl peroxide
  • the sanitary products obtained in this embodiment are thin and light, the lines and curves are smooth, and the tensile strength is up to 70 MPa, and the compressive and flexural strengths exceed 100 MPa.
  • the unsaturated polyester resin in this embodiment adopts the upper weft 928 produced by Shangwei Enterprise Co., Ltd., and the unsaturated resin has a solid content of 35% to 40%, and the rest is styrene; the polyester anti-shrinkage agent adopts the upper weft.
  • the Shangwei 7310 produced by Enterprise Co., Ltd. has a polyester solid content of 63% ⁇ 67%, and the rest is styrene.
  • Example 2 16% unsaturated polyester resin (upper weft 928), 12% polyester anti-shrinkage agent (upper weft 7310), 5% polyphosphazene micron fiber (length 3 ⁇ 6mm), 10% polyester fiber (length 5 ⁇ 10mm), 15% 1200 mesh wollastonite particles, 32% 1000 mesh calcium carbonate powder, 8% aluminum hydroxide powder, 3% color paste, 1% initiator.
  • the sanitary ware products obtained in this embodiment have excellent flame retardant performance and reach UL94V-0 grade. Colleagues have the characteristics of high temperature resistance and corrosion resistance, and can maintain the normal temperature state without feeling cold.
  • the polyphosphazene microfibers in this example are reinforcing fibers which serve to enhance the strength and toughness of the product.
  • Example 3 16% polyphosphazene modified unsaturated polyester resin (diphenoxy polyphosphazene), 12% polyester anti-shrinkage agent (upper weft 7310), 6% nylon fiber (length 3 ⁇ 5 mm) , 12% polyester fiber (length 5 ⁇ 10mm), 20% 1200 mesh wollastonite particles, 32% 1000 mesh calcium carbonate powder, 3% color paste, 1% initiator.
  • the water contact angle of the sanitary product in the embodiment reaches 95°, the waterproof performance is obviously improved, the surface of the product is not easily accumulated, the self-cleaning effect is obtained, the hardness is high, and the impact resistance and wear resistance are also ideal.
  • the percentages in the above embodiments are all percentage by mass, and the sanitary products in the embodiment may be a washbasin, a bathtub, a toilet, a bidet, a urinal, a shower tub, and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Public Health (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Non-Flushing Toilets (AREA)
  • Sanitary Device For Flush Toilet (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Description

一种树脂基复合材料洁具及其制备方法 技术领域
本发明涉及一种洁具， 尤其涉及一种以树脂和硅灰石为主要原料的复合 材料的洁具， 本发明还公开了该洁具的制备方法。 背景技术
常见的洁具包括浴缸、 台盆、 座便器、 小便斗及浴缸， 采用陶瓷制作， 陶瓷需要烧制， 对环境不友好， 同时生成工艺中要应用到很多稀土资源， 而 稀土矿产资源比较稀缺， 长此以往， 势必会有对矿产资源产生一定压力。
近来， 又有采用人造玛瑙或亚克力来制备卫浴洁具的， 见专利号为
ZL200410040962.6的中国发明专利《采用浇注工艺生成的亚克力座便器》（授 权公告号： CN126923C), 该专利中座便器零部件均采用树脂和玛瑙粉混合 物实心浇注在夹层空壳中的方式来制备座便器， 所得产品虽然具有陶瓷制品 的一般特性， 但该方法工艺复杂， 成本较高， 而且厚度有限， 自洁性不佳。 在此基础， 又公开了另一种亚克力和玻璃钢复合结构的座便器， 见专利号为 ZL200620034821.8的中国实用新型专利《亚克力和玻璃钢复合结构座便器》 (授权公告号： CN2926350Y)。
再参见中国发明专利申请号为 96106392.0的中国发明专利申请公开 《人 造大理石制品及其制备方法》（公开号： CN1167741A), 该申请以大理石粉、 不饱和聚酯树脂、 氢氧化铝及硅灰石为主要原料通过浇注工艺完成， 产品性 能和制备过程都得到了提高。 发明的公开
本发明所要解决的技术问题是针对上述的技术现状而另外提供一种高韧 性和强强度、 低成本的树脂基复合材料洁具。
本发明所要解决的又一个技术问题是提供一种节能环保、 低成本的树脂 基复合材料洁具的制备方法。
确 认 本 本发明解决上述技术问题所采用的技术方案为： 一种树脂基复合材料洁 具， 其特征在于采用原料经过混合、 注射、 模具固化而制得， 所述原料的组 分及其重量配比如下：
不饱和聚酯树脂 14%~30%；
聚酯型防收缩剂 6%~14%;
增强纤维 11%~37%；
硅灰石 10%~20%；
碳酸钙 25%~40%；
引发剂 0.8%~2.4%。
为便于后续的混合均匀， 所述的不饱和聚酯树脂由苯乙烯稀释不饱和树 脂而制得， 其中苯乙烯和不饱和树脂的重量配比满足：
苯乙烯 60%~65%；
不饱和树脂 35%~40%。
所述的不饱和树脂可以是邻苯型不饱和聚酯树脂或间苯型不饱和聚酯树 脂。
为便于后续的混合均匀， 所述的聚酯型防收缩剂由苯乙烯稀释具有防收 縮功能的聚酯而制得， 其中苯乙烯和聚酯的重量配比满足：
苯乙烯 33%~37%；
聚酯 63%~67%。
所述的增强纤维可以是尼龙纤维或聚聚膦腈微米纤维。
所述的原料中还包括重量配比为 1%~4%的色浆，用于调制各种颜色的卫 浴产品。
所述的原料中还包括重量配比为 6%~10%的氢氧化铝， 可以增加产品的 质感及阻燃性。
作为优选， 所述的引发剂包括过氧苯甲酸叔丁酯和过氧苯甲酰， 并且满 足过氧苯甲酸叔丁酯与过氧苯甲酰的重量配比为 1 : 2。
一种制备树脂基复合材料洁具的方法， 其特征在于包括如下步骤：
①、 取各原料组分并混合搅拌均匀成团状复合材料；
②、 将上述的复合材料注入热固性塑机的注射设备中；
③、 将复合材料注射到模具中， 加热， 保持温度 130°C~150°C， 保压固 化；
④、 打开模具， 取出成品。
作为优选， 于步骤③中模具进行抽取真空， 真空度为- 0.06〜- 0.09帕， 注 射时采用高压注射，射胶压力为每平方厘米 100千克，注射后固化保压时间为 2~3分钟以上。
与现有技术相比， 本发明的优点在于： 采用廉价的硅灰石和碳酸钙为主 要原料， 通过高压注射到模具内固化制得， 所以原料易得， 成本低廉， 无需 高能耗烧制， 能耗降低， 劳动强度也减轻， 采用热固性塑机注射， 劳动效率 高， 产品易于规模化生产， 次品率低； 另外， 所得产品外表光洁如镜， 自洁 性佳， 表面不沾污， 能保持常温状态， 手感无冰冷之感； 整体产品较轻， 且 具有高韧性和高强度的优点。 实现本发明的最佳方式
以下结合实施例对本发明作进一步详细描述。
制备昆仑晶石卫浴产品的方法主要包括以下几个步骤：
①、 用高性能改性的不饱和聚酯树脂混入昆仑晶石粉料（主要成分为硅 灰石）和各种粒径的颗粒、 聚脂纤维、 尼龙纤维、 颜料和引发剂， 经捏和机 搅拌捏合成团状复合材料；
②、 将团状复合材料注入特制的注射设备的料桶中；
③、 根据所生产的单个卫浴产品的材料用量输入热固性塑机电脑控制程 序中， 定量射出机构采用活塞式机筒高压注入卫浴金属模具中；
④、 卫浴产品的金属注射模具采用油导入加热， 加热温度保持在 130°C ~150°C， 对卫浴产品的金属模具抽取真空， 真空度为 -0.06〜- 0.09帕斯卡， 使 所生产的卫浴产品密实无气孔；
⑤、复合材料高压注射进金属模具中， 高温加热固化和保压 2分钟， 可消 除产品收縮变形；
⑥、 卫浴产品固化后用机械打开金属模具， 使用顶出装置把产品从模具 中顶出， 然后用机械手把卫浴产品从模具中取出放置于产品检验和包装流水 线上。
以下为各个配方不同的实施例。 实施例 18%不饱和聚酯树脂， 10%聚酯型防收縮剂， 20%尼龙纤维（长 度 3~5mm),一尼龙纤维为增强纤维， 10%聚脂纤维 （长度 5~10mm), 聚脂纤 维也为增强纤维， 13%的 1200目硅灰石微粒， 27%的 1000目碳酸钙粉料， 3% 色浆， 1%引发剂。引发剂采用氧苯甲酸叔丁酯（TBPB)和过氧苯甲酰（BPO)， 并且满足过氧苯甲酸叔丁酯和过氧苯甲酰的重量配比为 1 : 2。 本实施例制得 的卫浴产品薄而轻， 线条和弧形流畅， 而且抗张拉强度可达 70Mpa， 抗压和 抗弯强度都超过 100Mpa。
本实施例中的不饱和聚酯树脂采用上纬企业股份有限公司生产的上纬 928， 其不饱和树脂固含量为 35%~40%， 其余为苯乙烯； 聚酯型防收縮剂采 用上纬企业股份有限公司生产的上纬 7310， 其聚酯固含量为 63%~67%， 其余 为苯乙稀。
实施例 2: 16%不饱和聚酯树脂（上纬 928)， 12%聚酯型防收缩剂 （上纬 7310)， 5%聚膦腈微米纤维 （长度 3~6mm)， 10%聚脂纤维 （长度 5~10mm)， 15%1200目硅灰石颗粒， 32%1000目碳酸钙粉料， 8%氢氧化铝粉料， 3%色浆， 1%引发剂。本实施例制得的卫浴产品具有优异的阻燃性能，达到 UL94V-0级， 同事， 具有耐高温、耐腐蚀的特点， 另外能保持常温状态， 手感无冰冷之感。 本实施例中的聚膦腈微米纤维均为增强纤维， 起到增强产品强度和韧度的作 用。
实施例 3: 16%聚膦腈改性不饱和聚酯树脂 （二苯氧基聚膦腈）， 12%聚 酯型防收缩剂（上纬 7310)， 6%尼龙纤维（长度 3~5mm)， 12%聚脂纤维（长 度 5~10mm)， 20%的 1200目硅灰石颗粒， 32%1000目碳酸钙粉料， 3%色浆， 1%引发剂。本实施例中的卫浴产品水接触角达到 95° ， 防水性能得到明显提 高， 产品表面不容易积污， 有自洁作用， 硬度较高， 耐冲击和耐磨性也比较 理想。
以上实施例中的百分比均为质量百分比， 实施例中的卫浴产品可以是洗 脸盆、 浴缸、 座便器、 净身器、 小便斗、 淋浴盆等。

Claims

权利要求
1. 一种树脂基复合材料洁具 其特征在于， 采用原料经过混合、 注射、 模 具固化而制得， 所述原料的组分及其重量配比如下：
不饱和聚酯树脂 14%~30%;
聚酯型防收缩剂 6%~14%;
增强纤维 11%~37%；
硅灰石 10%~20%；
碳酸钙 25%~40%；
引发剂 0.8%~2.4%。
2. 根据权利要求 1所述的树脂基复合材料洁具, 其特征在于， 所述的不饱 和聚酯树脂由苯乙烯稀释不饱和树脂而制得, 其中苯乙烯和不饱和树脂 的重量配比满足：
苯乙烯 60%〜65%；
不饱和树脂 35%~40%。
3. 根据权利要求 2所述的树脂基复合材料洁具， 其特征在于， 所述的不饱 和树脂为邻苯型不饱和聚酯树脂或间苯型不饱和聚酯树脂。
4. 根据权利要求 1所述的树脂基复合材料洁具， 其特征在于， 所述的聚酯 型防收缩剂由苯乙烯稀释具有防收縮功能的聚酯而制得，其中苯乙烯和 聚酯的重量配比满足：
苯乙烯 33%~37%；
63%~67%。 根据权利要求 1所述的树脂基复合材料洁具， 其特征在于， 所述的增强 纤维为尼龙纤维或聚膦腈微米纤维。
6. 根据权利要求 1所述的树脂基复合材料洁具， 其特征在于， 所述'的原料 中还包括重量配比为 1%~4%的色浆。
7. 根据权利要求 1所述的树脂基复合材料洁具， 其特征在于， 所述的原料 中还包括重量配比为 6%~10%的氢氧化铝。
8. 根据权利要求 1所述的树脂基复合材料洁具， 其特征在于， 所述的引发 剂包括过氧苯甲酸叔丁酯和过氧苯甲酰，并且满足过氧苯甲酸叔丁酯与 过氧苯甲酰的重量配比为 1 : 2。
9. 一种制备权利要求 1~6树脂基复合材料洁具的方法， 其特征在于，包括 如下步骤：
①、 取各原料组分并混合搅拌均匀成团状复合材料；
②、 将上述的复合材料注入热固性塑机的注射设备中；
③、 将复合材料注射到模具中， 加热， 保持温度 130°C~150°C， 保压固 化；
④、 打开模具， 取出成品。
10.根据权利要求 9所述的方法， 其特征在于， 步骤③模具进行抽取真空， 真空度为 -0.06〜- 0.09 帕， 注射时采用高压注射， 射胶压力为每平方厘 米 100千克， 注射后固化保压时间为 2~3分钟以上。
PCT/CN2010/000030 2009-10-22 2010-01-08 一种树脂基复合材料洁具及其制备方法 WO2011047521A1 (zh)

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