JPH049176B2 - - Google Patents
Info
- Publication number
- JPH049176B2 JPH049176B2 JP58217952A JP21795283A JPH049176B2 JP H049176 B2 JPH049176 B2 JP H049176B2 JP 58217952 A JP58217952 A JP 58217952A JP 21795283 A JP21795283 A JP 21795283A JP H049176 B2 JPH049176 B2 JP H049176B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- refractive index
- glass
- sio
- cao
- 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
- 239000011521 glass Substances 0.000 claims description 47
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 28
- 239000000945 filler Substances 0.000 claims description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 229920003002 synthetic resin Polymers 0.000 claims description 13
- 239000000057 synthetic resin Substances 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims 2
- 239000000203 mixture Substances 0.000 description 42
- 239000000047 product Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004744 fabric Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 238000010828 elution Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910017976 MgO 4 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は特に透明感のある合成樹脂成形品を製
造するために有用な充填材に関するものである。
従来、例えばバスタブ、便器等の合成樹脂成形
品にガラス系充填材を混合して機械的強度、耐水
性、耐蝕性を改良することが行われている。そし
てこのような熱硬化性樹脂成形品に透明感を与え
ることは意匠的にみて極めて望ましいものであ
る。
本発明は上記のように熱硬化性樹脂成形品に望
ましい透明感を与えること、および該透明感を長
期にわたつて維持し、もつて合成樹脂成形品の市
場性を高めることを目的とするものである。
上記目的を達成するために本発明者等は鋭意研
究を重ねた結果、下記の組成のガラスからなる充
填材が最とも適したものであることを見出した。
SiO2 45〜70重量％（以下単に％とする）
B2O3 １〜９重量％
R2O ５〜15重量％
MO 15〜35重量％
Al2O3 ０〜10重量％
ここにＲはアルカリ金属であり、R2Oは一種も
しくは二種以上のアルカリ金属酸化物の混合物で
あつてもよく、ＭはMg、Ca、BaおよびZnから
選ばれた金属であり、MOは一種もしくは二種以
上の該金属の酸化物の混合物であつてもよい。
SiO2は化学耐久性に重要な成分であり、SiO2
の含有量が45％以下では化学耐久性に劣るガラス
しか得られない。しかし70％以上の含有量ではガ
ラスが高融点になりフリツト化に高温を要する。
B2O3とMOとはガラスの屈折率に関与する成
分であり、B2O3は屈折率を下げる方向に関与し、
MOは屈折率を上げる方向に関与する。各種合成
樹脂に近い屈折率を得るためにはMOが15〜35％
の範囲であることが必要であり、なかんづくCaO
はガラスの屈折率を大きくするために重要な成分
でありCaOがMO全体の40重量％以上を占めるこ
とが必要である。特にMOが上記範囲において少
なくなるとCaOの割合を増やす必要がある。
B2O3は屈折率の補助的調整要素として１〜９％
の範囲で添加されるが、含有量が９％以上になる
と屈折率が低くなり過ぎ調整が困難になり、また
得られる成形品の耐酸性、耐アルカリ性、耐熱水
性等に悪影響を及ぼす。
R2Oはフリツト化する為の融剤としての作用を
するものであり、R2Oの含有量が５％以下では融
剤効果が乏しくなり、15％以上の含有量ではガラ
スの耐久性に悪影響を及ぼす。
Al2O3は化学耐久性および屈折率に対して助長
効果をもたらすために添加されるが、含有量が10
％を越えるとガラスの融点が高くなり、フリツト
化に高温を要する。
上記組成において、SiO2／B2O3は７〜35の範
囲の重量比とする。そしてSiO2／B2O3が７を下
廻るとガラスの耐水性が悪くなり、SiO2／B2O3
が35を上廻るとフリツト化が困難である。また
SiO2／B2O3が上記範囲であると屈折率が所定の
範囲に調節し易い。
上記組成範囲のガラスは屈折率が1.45〜1.65の
範囲にあり、この種の成形品に多用される例えば
ポリエステル樹脂の屈折率1.52〜1.57、アクリル
樹脂の屈折率1.48〜1.57、エポキシ樹脂の屈折率
1.61、フエノール樹脂の屈折率1.50〜1.58、尿素
樹脂の屈折率1.54〜1.56、ポリカーボネートの屈
折率1.586、ポリスチレンの屈折率1.59〜1.60、ポ
リエチレンの屈折率1.54、ポリプロピレンの屈折
率1.49、ポリアセタールの屈折率1.48、ナイロン
の屈折率1.53等に一致もしくは極めて近似するも
のであり、これら合成樹脂の成形品に混合されて
極めて良好な透明感を与えるものである。
本発明の充填材は粉末状、繊維状、片状等任意
の形状で提供されるものである。そして繊維状の
場合には不織布あるいは編織物とされてもよい。
本発明の充填材は上記したように合成樹脂の成
形品に添加されて極めて良好な透明感を与えるも
のであるが、該透明感を維持するには更に上記組
成のガラス表面にシラン処理を施こした充填材を
用いることが必要である。該シラン処理とはシラ
ンカツプリング剤、シリコン樹脂、オルガノポリ
シロキサン等の珪素化合物によつてガラス表面を
処理することを言う。該シラン処理は具体的には
上記例示したような珪素化合物を0.5〜50％、望
ましくは0.7〜10％の水および／または有機溶剤
溶液にガラスを浸漬させた後、常温で乾燥、ある
いは所望なれば150〜250℃程度の温度で熱処理を
行うことにより実施される。かくしてシラン処理
を施こせば合成樹脂とガラスとの結合力が強化さ
れ、合成樹脂とガラスとの剥離にもとづく白化現
象のような透明感を阻害するような要因は排除さ
れ、長期にわたつて透明感を維持することが出来
る。
以上本発明によれば上記組成のガラスは屈折率
が各種合成樹脂と実質的に一致し、したがつて充
填材として成形品に添加されて極めて優れた透明
感が得られ、該透明感は該ガラス表面をシラン処
理することによつて長期間にわたつて維持される
が、上記組成のガラスはまた耐熱水性、耐寒性、
耐薬品性にも優れ、キツチンカウンター、浴槽、
便器、洗面化粧台、流し台、壁材、床材等に有用
な市場性の高い合成樹脂成形品を提供する。
実験１（B2O3溶出試験）
次の組成をベース組成としてB2O3の含有量を
種々に変えたガラス粉末（平均粒径50μ前後）を
作成し、該ガラス粉末の50ｇを500mlの蒸留水中
に入れ、室温（20℃）および60℃にて６時間撹拌
し、上澄液中に溶出したB2O3の濃度（μｇ／ml）
を分析した。該実験は３回繰返して行われ、その
結果を第１表、第１図および第２図に示す。
ベース組成
SiO2 55重量部
Na2O 10重量部
K2O ２重量部
CaO 20重量部
Al2O3 ３重量部
溶出試験結果
The present invention particularly relates to a filler useful for producing transparent synthetic resin molded articles. Conventionally, glass fillers have been mixed into synthetic resin molded products such as bathtubs and toilet bowls to improve their mechanical strength, water resistance, and corrosion resistance. From a design point of view, it is extremely desirable to impart transparency to such thermosetting resin molded articles. As mentioned above, the present invention aims to provide desirable transparency to thermosetting resin molded products, maintain this transparency over a long period of time, and thereby increase the marketability of synthetic resin molded products. It is. In order to achieve the above object, the present inventors have conducted extensive research and have found that a filler made of glass having the following composition is the most suitable. SiO 2 45-70% by weight (hereinafter simply referred to as %) B 2 O 3 1-9% by weight R 2 O 5-15% by weight MO 15-35% by weight Al 2 O 3 0-10% by weight Here R is is an alkali metal, R 2 O may be one or a mixture of two or more alkali metal oxides, M is a metal selected from Mg, Ca, Ba, and Zn, and MO is one or two alkali metal oxides. It may be a mixture of the above metal oxides. SiO 2 is an important component for chemical durability, and SiO 2
If the content is less than 45%, only glass with inferior chemical durability can be obtained. However, if the content exceeds 70%, the glass has a high melting point and requires high temperatures to form into a frit. B 2 O 3 and MO are components that are involved in the refractive index of glass, and B 2 O 3 is involved in lowering the refractive index,
MO is involved in increasing the refractive index. To obtain a refractive index close to that of various synthetic resins, MO should be 15 to 35%.
It is necessary that the CaO
CaO is an important component to increase the refractive index of glass, and it is necessary that CaO accounts for 40% by weight or more of the entire MO. In particular, when MO decreases within the above range, it is necessary to increase the proportion of CaO.
B 2 O 3 is 1-9% as an auxiliary adjustment element for refractive index
However, if the content exceeds 9%, the refractive index becomes too low and adjustment becomes difficult, and it also has a negative effect on the acid resistance, alkali resistance, hot water resistance, etc. of the resulting molded product. R 2 O acts as a fluxing agent for fritting, and if the R 2 O content is less than 5%, the fluxing effect will be poor, and if the content is more than 15%, the durability of the glass will be affected. Adversely affect. Al 2 O 3 is added to have a supportive effect on chemical durability and refractive index, but when the content is 10
%, the melting point of the glass becomes high and a high temperature is required for fritting. In the above composition, the weight ratio of SiO 2 /B 2 O 3 is in the range of 7 to 35. When SiO 2 /B 2 O 3 is less than 7, the water resistance of the glass deteriorates, and SiO 2 /B 2 O 3
If it exceeds 35, it is difficult to make it into a frit. Also
When SiO 2 /B 2 O 3 is within the above range, the refractive index can be easily adjusted to a predetermined range. Glasses with the above composition range have a refractive index in the range of 1.45 to 1.65, and are often used in this type of molded product.For example, polyester resin has a refractive index of 1.52 to 1.57, acrylic resin has a refractive index of 1.48 to 1.57, and epoxy resin has a refractive index of 1.45 to 1.65.
1.61, refractive index of phenolic resin 1.50-1.58, refractive index of urea resin 1.54-1.56, refractive index of polycarbonate 1.586, refractive index of polystyrene 1.59-1.60, refractive index of polyethylene 1.54, refractive index of polypropylene 1.49, refractive index of polyacetal 1.48, and nylon's refractive index of 1.53, etc., and when mixed into molded products made of these synthetic resins, it gives extremely good transparency. The filler of the present invention is provided in any shape such as powder, fiber, flake, etc. In the case of a fibrous material, it may be made into a nonwoven fabric or a knitted fabric. As mentioned above, the filler of the present invention is added to a synthetic resin molded product to give it an extremely good transparency, but in order to maintain the transparency, the glass surface of the above composition must be further treated with silane. It is necessary to use strained filler. The silane treatment refers to treatment of the glass surface with a silicon compound such as a silane coupling agent, silicone resin, or organopolysiloxane. Specifically, the silane treatment is performed by immersing the glass in a water and/or organic solvent solution of 0.5 to 50%, preferably 0.7 to 10%, of a silicon compound such as those exemplified above, and then drying at room temperature, or as desired. For example, heat treatment is performed at a temperature of about 150 to 250°C. In this way, silane treatment strengthens the bond between the synthetic resin and glass, eliminates factors that impede transparency, such as the whitening phenomenon caused by peeling of the synthetic resin and glass, and maintains transparency for a long time. It is possible to maintain the feeling. As described above, according to the present invention, the refractive index of the glass having the above-mentioned composition is substantially the same as that of various synthetic resins, and therefore, when added to molded products as a filler, extremely excellent transparency can be obtained; Although it is maintained over a long period of time by silane treatment of the glass surface, the glass with the above composition also has hot water resistance, cold resistance,
Excellent chemical resistance, suitable for kitchen counters, bathtubs,
We provide highly marketable synthetic resin molded products that are useful for toilet bowls, vanities, sinks, wall materials, floor materials, etc. Experiment 1 (B 2 O 3 elution test) Using the following composition as a base composition, glass powders (average particle size around 50μ) with various B 2 O 3 contents were prepared, and 50 g of the glass powder was poured into 500 ml of Concentration (μg/ml) of B 2 O 3 eluted into the supernatant after being placed in distilled water and stirred at room temperature (20°C) and 60°C for 6 hours.
was analyzed. The experiment was repeated three times and the results are shown in Table 1, Figures 1 and 2. Base composition SiO 2 55 parts by weight Na 2 O 10 parts by weight K 2 O 2 parts by weight CaO 20 parts by weight Al 2 O 3 3 parts by weight Elution test results
【表】
第１表、第１図および第２図によればB2O3の
含有量が本発明の限定範囲（10重量部以上）を越
えかつSiO2／B2O3が７を下廻るとB2O3の溶出量
が急激に増加することが明らかである。
実験２（屈折率の組成依存）
次の組成をベースとしてMO含有量を種々に変
えたガラスを作成し屈折率を測定した。但しMO
はCaO：BaO＝１：１とする。その結果を第２
表および第３図に示す。
ベース組成１
SiO2 50重量部
Na2O 10重量部
K2O ２重量部
Al2O3 ３重量部
B2O3 ５重量部
ベース組成２
SiO2 50重量部
Na2O 10重量部
K2O ２重量部
Al2O3 ３重量部
B2O3 10重量部
ベース組成３
SiO2 50重量部
Na2O 10重量部
K2O ２重量部
Al2O3 ３重量部
B2O3 15重量部[Table] According to Table 1, Figures 1 and 2, the B 2 O 3 content exceeds the limited range of the present invention (10 parts by weight or more) and the SiO 2 /B 2 O 3 ratio is less than 7. It is clear that the amount of B 2 O 3 eluted increases rapidly as the rotation of the tube increases. Experiment 2 (composition dependence of refractive index) Glasses with various MO contents were prepared based on the following composition, and the refractive index was measured. However, MO
is CaO:BaO=1:1. The result is the second
It is shown in the table and FIG. Base composition 1 SiO 2 50 parts by weight Na 2 O 10 parts by weight K 2 O 2 parts by weight Al 2 O 3 3 parts by weight B 2 O 3 5 parts by weight Base composition 2 SiO 2 50 parts by weight Na 2 O 10 parts by weight K 2 O 2 parts by weight Al 2 O 3 3 parts by weight B 2 O 3 10 parts by weight Base composition 3 SiO 2 50 parts by weight Na 2 O 10 parts by weight K 2 O 2 parts by weight Al 2 O 3 3 parts by weight B 2 O 3 15 Weight part
【表】
第２表および第３図に示すようにB2O3を本発
明に限定範囲以内で含むベース組成１においては
MOと屈折率との関係がMOが15〜35重量部の範
囲で略線型になり、しかもその範囲で屈折率は
1.45〜1.65の範囲に入る。したがつてベース組成
１ではMOの量で屈折率を調節することが容易で
ある。しかしB2O3を本発明の限定範囲以上で含
むベース組成２、３ではMOと屈折率との関係が
非線型になり、更にMOの低含有領域では屈折率
が1.45を下廻る。
実験３（屈折率の組成依存）
次に組成においてMOをCaO＋BaOとしてCaO
のMO中の重量％を種々に変えたガラスを作成し
屈折率を測定した。その結果を第３表に示す。
SiO2 60重量％
Na2O 10重量％
K2O ２重量％
MO 20重量％
Al2O3 ３重量％
B2O3 ５重量％[Table] As shown in Table 2 and Figure 3, in base composition 1 containing B 2 O 3 within the limited range according to the present invention,
The relationship between MO and refractive index is approximately linear in the range of 15 to 35 parts by weight of MO, and the refractive index is
It falls in the range of 1.45 to 1.65. Therefore, with base composition 1, it is easy to adjust the refractive index by adjusting the amount of MO. However, in base compositions 2 and 3 containing B 2 O 3 in an amount greater than the limited range of the present invention, the relationship between MO and refractive index becomes nonlinear, and furthermore, in a low MO content region, the refractive index falls below 1.45. Experiment 3 (composition dependence of refractive index) Next, in the composition, MO is CaO + BaO and CaO
Glasses with various weight percentages of MO in MO were prepared and their refractive indices were measured. The results are shown in Table 3. SiO 2 60% by weight Na 2 O 10% by weight K 2 O 2% by weight MO 20% by weight Al 2 O 3 3% by weight B 2 O 3 5% by weight
【表】
第３表に示すようにMO中にCaOが40重量％以
下含まれているガラスは屈折率が1.45以下にな
る。
実施例 １
次の組成ガラス粉末を充填材とする。
SiO2 58％
B2O3 ７％
Na2O ８％
K2O １％
CaO 26％
上記充填材の屈折率は1.55である。
上記充填材300ｇを不飽和ポリエステル：スチ
レン単量体の１：１混合物700ｇと混合し、該混
合物に更にメチルエチルケトンハイドロパーオキ
サイド0.5ｇを添加し真空脱泡しつつ混練する。
該混練物を所定の鋳型中に流しこみ、70℃３時間
の加熱により透明性の良好な成形物を得る。
実施例 ２
次の組成のガラス繊維でガラスクロスを作成す
る。
SiO2 55％
B2O3 ７％
Na2O ７％
K2O ３％
CaO 27％
Al2O3 ２％
上記ガラスクロスの屈折率は1.57である。
上記ガラスクロスをシランカツプリング剤とし
てビニルトリメトキシシランの５％トルエン溶液
に含浸し、含浸後10分間の風乾の後100℃５分の
加熱乾燥を行う。かくしてシラン処理を施こした
ガラスクロスによつて成形型中で実施例１の合成
樹脂原料を用いてハンドレイアツプ法にて成形物
を成形する。該成形物は良好な透明感を有し該透
明感は該成形物を80℃の温水に400時間浸漬した
後も維持される。
実施例 ３
次の組成のガラス小片を用いる。
SiO2 55％
B2O3 ３％
Na2O 10％
K2O ３％
CaO 20％
Al2O3 ９％
上記ガラス小片の屈折率は1.53である。
上記ガラス小片をシリコン油（オルガノポリシ
ロキサン：信越化学社製KF−96）に浸漬し浸漬
後200℃10分間の熱処理を行う。かくして得られ
た充填材400ｇをポリエチレン600ｇの溶融物と混
合し、ペレタイザーによつてペレツト化して成形
用コンパウンドを得る。該コンパウンドは射出成
形、押出成形等によつて透明性良好な成形品を得
る。
実施例 ４
実施例１のガラス粉末に代えて次の組成のガラ
ス粉末を充填材とし、実施例１と同様にして透明
性の良好な成形物を得る。
SiO2 60％
B2O3 ５％
Na2O ７％
K2O ２％
CaO 12％
BaO ５％
ZnO ９％
上記ガラス粉末の屈折率は1.58である。
実施例 ５
次の組成のガラス繊維を作成する。
SiO2 55％
B2O3 ７％
Na2O 12％
K2O ２％
CaO 10％
MgO ４％
Al2O3 ７％
ZnO ３％
上記ガラス繊維の屈折率は1.50である。
上記ガラス繊維をシランカツプリング剤として
ビニルトリメトキイシシランの５％トルエン溶液
に含浸し、含浸後10分間の風乾の後100℃５分の
加熱乾燥を行う。かくしてシラン処理を施したガ
ラス繊維300ｇをポリプロピレン700ｇの溶融物と
混合し、鋳込法により透明性良好な成形品を得
る。
実施例 ６
実施例３のガラス小片に代えて次の組成のガラ
ス小片を用いて実施例３と同様にして透明性良好
な成形品を得る。
SiO2 60％
B2O3 ３％
Na2O ９％
CaO 25％
ZnO ２％
MgO １％
上記ガラス小片の屈折率は1.55である。
実施例 ７
次の組成のガラス粉末を充填材とする。
SiO2 55％
B2O3 ２％
Na2O ３％
K2O ３％
CaO 25％
BaO ７％
Al2O3 ５％
上記充填材の屈折率は1.60である。
上記充填材300ｇをエポキシ樹脂700ｇと混合
し、該混合物に更にポリアミン10ｇを添加し真空
脱泡しつつ混練する。該混練物を所定の鋳型中に
流しこみ室温で10時間硬化させれば透明性の良好
な成形物を得る。
比較例 １
次の組成のガラス粉末を充填材として実施例１
と同様に成形物を作成する。
SiO2 55％
B2O3 ５％
Na2O ５％
K2O 18％
CaO 12％
上記組成の充填材はCaOを本発明の限定範囲の
15％を下回る量で含み、屈折率が1.42と低く成形
物の透明感は良好でない。
比較例 ２
次の組成のガラス粉末を充填材として実施例１
と同様に成形物を作成する。
SiO2 50％
B2O3 ３％
Al2O3 ６％
Na2O ６％
CaO 30％
BaO ７％
上記組成の充填材はCaO＋BaOを本発明の限
定範囲の35％を上回る量で含み、屈折率が1.68と
高く成形物の透明感は良好でない。
比較例 ３
次の組成のガラス粉末はNa2Oを本発明の限定
範囲の５％を下回る量で含み、フリツト化に高温
を要し困難である。
Si2O3 65％
B2O3 ５％
Al2O3 ７％
Na2O ４％
CaO 17％
MgO ２％
比較例 ４
次の組成のガラス粉末はNa2Oを本発明の限定
範囲の15％を上回る量で含み、耐久性に劣る。
Si2O3 45％
B2O3 ５％
Al2O3 ８％
Na2O 18％
CaO 24％
比較例 ５
次の組成のガラス粉末を充填材とする。
SiO2 53％
B2O3 12％
Na2O ８％
K2O １％
CaO 26％
上記充填材の屈折率は1.46である。
上記充填材を用いて実施例１と同様にして成形
物を製造したが、該成形物の透明性は充分なもの
ではなかつた。
比較例 ６
次の組成のガラス繊維でガラスクロスを作成す
る。
SiO2 50％
B2O3 12％
Na2O ７％
K2O ３％
CaO 27％
Al2O3 ２％
上記ガラスクロスの屈折率は1.48である。
上記充填材を用いて実施例２と同様にして成形
物を製造したが、該成形物の透明性は充分なもの
ではなかつた。
耐熱水性試験
実施例１、２および比較例５、６の成形物を用
いて耐熱水性試験を行う。耐熱水性試験は各成形
物について厚さ５mm、50×50mmのテストピースを
作成し、100℃の沸騰水中に100時間浸漬した後の
テストピース表面の状態を目視により観察する。
試験結果は下表の通りである。
テストピース 表面の状態
実施例 １ 変化なし
２ 変化なし
比較例 ５ 黄 変
６ 黄 変
上記試験により、B2O3を本発明の限定範囲を
越えて含有する比較例５、６の充填材を用いた成
形物は耐熱水性に劣るが、B2O3を本発明の限定
範囲内で含有する実施例１、２の充填材を用いた
成形物は耐熱水性が良好である。[Table] As shown in Table 3, glasses containing 40% by weight or less of CaO in MO have a refractive index of 1.45 or less. Example 1 A glass powder having the following composition was used as a filler. SiO 2 58% B 2 O 3 7% Na 2 O 8% K 2 O 1% CaO 26% The refractive index of the above filler is 1.55. 300 g of the above filler is mixed with 700 g of a 1:1 mixture of unsaturated polyester and styrene monomers, and 0.5 g of methyl ethyl ketone hydroperoxide is added to the mixture, followed by kneading while defoaming in vacuum.
The kneaded product is poured into a predetermined mold and heated at 70° C. for 3 hours to obtain a molded product with good transparency. Example 2 A glass cloth is made from glass fibers having the following composition. SiO 2 55% B 2 O 3 7% Na 2 O 7% K 2 O 3% CaO 27% Al 2 O 3 2% The refractive index of the above glass cloth is 1.57. The above glass cloth was impregnated with a 5% toluene solution of vinyltrimethoxysilane as a silane coupling agent, and after the impregnation, it was air-dried for 10 minutes and then heated at 100° C. for 5 minutes. A molded article is molded using the synthetic resin raw material of Example 1 using the silane-treated glass cloth in a mold by the hand lay-up method. The molded product has good transparency, and this transparency is maintained even after the molded product is immersed in hot water at 80° C. for 400 hours. Example 3 Glass pieces having the following composition are used. SiO 2 55% B 2 O 3 3% Na 2 O 10% K 2 O 3% CaO 20% Al 2 O 3 9% The refractive index of the above glass piece is 1.53. The above-mentioned glass piece is immersed in silicone oil (organopolysiloxane: KF-96 manufactured by Shin-Etsu Chemical Co., Ltd.), and after immersion is heat-treated at 200° C. for 10 minutes. 400 g of the filler thus obtained is mixed with 600 g of melted polyethylene and pelletized using a pelletizer to obtain a molding compound. A molded article with good transparency can be obtained from the compound by injection molding, extrusion molding, or the like. Example 4 A molded article with good transparency is obtained in the same manner as in Example 1 except that glass powder having the following composition is used as a filler in place of the glass powder in Example 1. SiO 2 60% B 2 O 3 5% Na 2 O 7% K 2 O 2% CaO 12% BaO 5% ZnO 9% The refractive index of the above glass powder is 1.58. Example 5 A glass fiber having the following composition is prepared. SiO 2 55% B 2 O 3 7% Na 2 O 12% K 2 O 2% CaO 10% MgO 4% Al 2 O 3 7% ZnO 3% The refractive index of the above glass fiber is 1.50. The above glass fibers were impregnated with a 5% toluene solution of vinyltrimethoxysilane as a silane coupling agent, and after impregnating, air-dried for 10 minutes and then heated at 100° C. for 5 minutes. 300 g of the glass fibers thus treated with silane are mixed with 700 g of melted polypropylene, and a molded article with good transparency is obtained by casting. Example 6 A molded article with good transparency is obtained in the same manner as in Example 3 except that glass pieces having the following composition are used in place of the glass pieces of Example 3. SiO 2 60% B 2 O 3 3% Na 2 O 9% CaO 25% ZnO 2% MgO 1% The refractive index of the above glass piece is 1.55. Example 7 A glass powder having the following composition is used as a filler. SiO 2 55% B 2 O 3 2% Na 2 O 3% K 2 O 3% CaO 25% BaO 7% Al 2 O 3 5% The refractive index of the above filler is 1.60. 300 g of the above filler is mixed with 700 g of epoxy resin, 10 g of polyamine is further added to the mixture, and the mixture is kneaded while defoaming in vacuum. The kneaded product is poured into a predetermined mold and cured at room temperature for 10 hours to obtain a molded product with good transparency. Comparative Example 1 Example 1 using glass powder with the following composition as a filler
Create a molded object in the same way. SiO 2 55% B 2 O 3 5% Na 2 O 5% K 2 O 18% CaO 12% The filler with the above composition contains CaO within the limited range of the present invention.
It is contained in an amount of less than 15%, the refractive index is as low as 1.42, and the transparency of the molded product is not good. Comparative Example 2 Example 1 using glass powder with the following composition as a filler
Create a molded object in the same way. SiO 2 50% B 2 O 3 3% Al 2 O 3 6% Na 2 O 6% CaO 30% BaO 7% The filler with the above composition contains CaO + BaO in an amount exceeding 35% of the limited range of the present invention, and has a refractive index. The ratio is as high as 1.68, and the transparency of the molded product is not good. Comparative Example 3 A glass powder having the following composition contains Na 2 O in an amount less than 5% of the limited range of the present invention, and requires high temperature and is difficult to frit. Si 2 O 3 65% B 2 O 3 5% Al 2 O 3 7% Na 2 O 4% CaO 17% MgO 2% Comparative Example 4 Glass powder with the following composition contains Na 2 O within the limited range of the present invention. %, the durability is poor. Si 2 O 3 45% B 2 O 3 5% Al 2 O 3 8% Na 2 O 18% CaO 24% Comparative Example 5 A glass powder having the following composition was used as a filler. SiO 2 53% B 2 O 3 12% Na 2 O 8% K 2 O 1% CaO 26% The refractive index of the above filler is 1.46. A molded article was produced in the same manner as in Example 1 using the above filler, but the transparency of the molded article was not sufficient. Comparative Example 6 A glass cloth is made from glass fibers having the following composition. SiO 2 50% B 2 O 3 12% Na 2 O 7% K 2 O 3% CaO 27% Al 2 O 3 2% The refractive index of the above glass cloth is 1.48. A molded article was produced in the same manner as in Example 2 using the above filler, but the transparency of the molded article was not sufficient. Hot Water Resistance Test A hot water resistance test is conducted using the molded products of Examples 1 and 2 and Comparative Examples 5 and 6. In the hot water resistance test, a test piece of 5 mm thickness and 50 x 50 mm is prepared for each molded product, and the condition of the surface of the test piece is visually observed after being immersed in boiling water at 100°C for 100 hours.
The test results are shown in the table below. Test piece Surface condition Example 1 No change 2 No change Comparative example 5 Yellowing 6 Yellowing According to the above test, the fillers of Comparative Examples 5 and 6 containing B 2 O 3 exceeding the limited range of the present invention were used. The molded products using the fillers of Examples 1 and 2 containing B 2 O 3 within the limited range of the present invention have good hot water resistance.
第１図は室温におけるB2O3含有量とB2O3溶出
量との関係を示すグラフ、第２図は60℃における
B2O3含有量とB2O3溶出量との関係を示すグラ
フ、第３図はMOと屈折率との関係を示すグラフ
であり、図中・−・はベース組成１、ｘ−ｘはベ
ース組成２、△−△はベース組成３に関するグラ
フである。
Figure 1 is a graph showing the relationship between B 2 O 3 content and B 2 O 3 elution amount at room temperature, and Figure 2 is a graph showing the relationship between B 2 O 3 content and B 2 O 3 elution amount at room temperature.
Figure 3 is a graph showing the relationship between B 2 O 3 content and B 2 O 3 elution amount, and Figure 3 is a graph showing the relationship between MO and refractive index. is a graph regarding base composition 2, and Δ-Δ is a graph regarding base composition 3.
Claims (1)
R2O5〜15重量％（ここにＲはアルカリ金属であ
る）、MO15〜35重量％（ここにＭはMg、Ca、
BaおよびZnから選ばれた一種または二種以上の
金属である）、Al2O30〜10重量％の組成であつ
て、SiO2／B2O3が７〜35の範囲であり、CaOは
MO全体の40重量％以上を占めるガラスからなる
合成樹脂成形品用充填材 ２ SiO245〜70重量％、B2O31〜9.9重量％、
R2O5〜15重量％（ここにＲはアルカリ金属であ
る）、MO15〜35重量％（ここにＭはMg、Ca、
BaおよびZnから選ばれた一種または二種以上の
金属である）、Al2O30〜10重量％の組成であつ
て、SiO2／B2O3が７〜35の範囲であり、CaOは
MO全体の40重量％以上を占めるガラス表面にシ
ラン処理を施した合成樹脂成形品用充填材[Claims] 1 SiO 2 45-70% by weight, B 2 O 3 1-9% by weight,
R 2 O 5-15% by weight (where R is an alkali metal), MO 15-35% by weight (here M is Mg, Ca,
one or more metals selected from Ba and Zn), Al 2 O 3 0 to 10% by weight, SiO 2 /B 2 O 3 in the range of 7 to 35, CaO teeth
Filler 2 for synthetic resin molded products made of glass that accounts for 40% or more of the entire MO SiO 2 45 to 70% by weight, B 2 O 3 1 to 9.9% by weight,
R 2 O 5-15% by weight (where R is an alkali metal), MO 15-35% by weight (here M is Mg, Ca,
one or more metals selected from Ba and Zn), Al 2 O 3 0 to 10% by weight, SiO 2 /B 2 O 3 in the range of 7 to 35, CaO teeth
A filler for synthetic resin molded products whose glass surface is silane-treated, accounting for more than 40% by weight of the entire MO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21795283A JPS60127334A (en) | 1983-11-18 | 1983-11-18 | Filler for synthetic resin molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21795283A JPS60127334A (en) | 1983-11-18 | 1983-11-18 | Filler for synthetic resin molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60127334A JPS60127334A (en) | 1985-07-08 |
| JPH049176B2 true JPH049176B2 (en) | 1992-02-19 |
Family
ID=16712282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21795283A Granted JPS60127334A (en) | 1983-11-18 | 1983-11-18 | Filler for synthetic resin molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60127334A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2098566A1 (en) * | 1991-11-15 | 1993-05-16 | Masaya Okamoto | Polycarbonate resin composition and process for producing the same |
| JPH081998B2 (en) * | 1991-12-13 | 1996-01-10 | 東光株式会社 | Shield case with power transistor |
| JP6576096B2 (en) * | 2015-05-14 | 2019-09-18 | 凸版印刷株式会社 | Decorative sheet and method for producing the decorative sheet |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS512351A (en) * | 1974-05-23 | 1976-01-09 | Nippon Telegraph & Telephone | ENKAKUSOSASEISHIGAZOSATSUZOSOCHI |
| JPS5121951A (en) * | 1974-08-12 | 1976-02-21 | Matsushita Electric Works Ltd | HEAADORAIYA |
| JPS5123538A (en) * | 1974-08-21 | 1976-02-25 | Canon Kk | JUSHI SEIBUTSU |
| JPS5429538A (en) * | 1977-08-09 | 1979-03-05 | Toshiba Corp | Information processing system |
| JPS56148538A (en) * | 1980-04-19 | 1981-11-18 | Nippon Fueroo Kk | Molding of thermosetting resin |
| JPS57167358A (en) * | 1981-04-08 | 1982-10-15 | Chisso Corp | Silane-based inorganic filler-treating agent and inorganic filler |
-
1983
- 1983-11-18 JP JP21795283A patent/JPS60127334A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS512351A (en) * | 1974-05-23 | 1976-01-09 | Nippon Telegraph & Telephone | ENKAKUSOSASEISHIGAZOSATSUZOSOCHI |
| JPS5121951A (en) * | 1974-08-12 | 1976-02-21 | Matsushita Electric Works Ltd | HEAADORAIYA |
| JPS5123538A (en) * | 1974-08-21 | 1976-02-25 | Canon Kk | JUSHI SEIBUTSU |
| JPS5429538A (en) * | 1977-08-09 | 1979-03-05 | Toshiba Corp | Information processing system |
| JPS56148538A (en) * | 1980-04-19 | 1981-11-18 | Nippon Fueroo Kk | Molding of thermosetting resin |
| JPS57167358A (en) * | 1981-04-08 | 1982-10-15 | Chisso Corp | Silane-based inorganic filler-treating agent and inorganic filler |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60127334A (en) | 1985-07-08 |
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