JPH0481446A - Resin composition resistant to hot water - Google Patents

Abstract

PURPOSE:To obtain the subject composition giving a molded article having high resistance to hot water, excellent surface smoothness and high impact strength by compounding a post-chlorinated PVC having a specific chlorine content with an impact modifier, a heat stabilizer, a lubricant and an inorganic filler. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a post-chlorinated vinyl chloride resin (CPVC) having a chlorine- content of 67-71wt.% with (B) 5-10 pts.wt. of one or more impact modifiers selected from MBS resin, ABS resin and MABS resin, (C) 1-3 pts.wt. of mercapto-tin stabilizer, (D) 1-5 pts.wt. of a hydrophobic lubricant and (E) 0.2-1.0 pt.wt. of an inorganic filler having an average particle diameter of 400-10,000Angstrom . The softening point of the molded article of the composition is >=115 deg.C measured in conformity to JIS K7206-B. The water absorption by a heat-resistance acceleration test comprising the immersion in hot water of 110 deg.C for 60 days is <=20mg/cm<2> per unit surface area of the molded article.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a heat-resistant resin composition with improved hot water resistance that is used as an industrial material for hot water pipes, hot water tanks, etc. that come into contact with water at high temperatures. .

[Prior art and its problems]

Conventionally, post-chlorinated polyvinyl chloride resin (hereinafter referred to as CPVC) has been used as a heat-resistant material for hot water pipes, hot water tanks, etc. that come into contact with water at high temperatures.
Resin compositions containing living organisms have been used by being thermoformed into pipe or plate shapes. The CPVC used here has an improved softening temperature by subjecting ordinary vinyl chloride resin to an addition reaction with chlorine, and has a heat resistance that is 20 to 30 degrees Celsius higher than that of ordinary vinyl chloride resin. However, it has the drawbacks of poor processability during thermoforming and low impact strength.

Therefore, various methods have been proposed and put into practical use in order to overcome these drawbacks. For example, Tokuko Showa 3
B-12175 and Special Publication No. 44-939 have CPVC
A method is disclosed for improving processability and impact strength by blending chlorinated polyethylene with. In addition, the special public service 1977-193
No. 08 discloses a method of improving processability and impact strength by blending ABS resin, MBS resin, or MABS resin with CPVC.

However, the molded products obtained by the above method still do not have sufficient hot water resistance, and when exposed to hot water for a long period of time, there is a problem that weight increases due to water absorption and physical properties decrease as a result. .

As a CPVC composition with improved hot water resistance, Japanese Patent Publication No. 62-13987 discloses a composition in which CPVC and ordinary vinyl chloride resin are mixed. over ℃100~110
When exposed to hot water at a high temperature of 0.degree. C. for a long period of time, there is a problem that not only does the weight increase due to water absorption, but also a blister phenomenon (occurrence of water blisters) occurs on the surface.

The present invention aims to solve this problem and to solve the problem of 90°C in the industrial world in the future.
In view of the prediction that the use of high-temperature hot water will become increasingly necessary, the present invention aims to provide a heat-resistant material with excellent hot water resistance.

[Means for solving problems]

The inventors have demonstrated that cp exposed to hot water exceeding 90°C
As a result of investigating the factors that cause water absorption and blister phenomenon in V C & They discovered that the presence of the agent had an effect, and completed the present invention.

That is, the present invention includes a hot water-resistant resin composition characterized by comprising the following components (A) to (E): (A) CP with a chlorine content of 67 to 71% by weight; ~'010
0 parts by weight, (B) 5 to 10 parts by weight of at least one impact resistance reinforcing agent selected from MBS resin, ABS resin and MABS resin, (C) 1 to 3 parts by weight of mercaptotin-based thermal stabilizer, (D ) 1 to 5 parts by weight of a hydrophobic lubricant; (E) 0.2 to 1.0 parts by weight of an inorganic filler having an average particle diameter of 400 to 10,000 angstroms.

CPVC, which is the component (A) of the present invention, is a homopolymer of vinyl chloride or a predominant amount of vinyl chloride and at least one comonomer copolymerizable therewith, such as ethylene, propylene, vinyl acetate, vinylidene chloride, allyl chloride, etc. A copolymer with a minor amount of
% by weight. The use of CPVC with a chlorine content of 67 to 71% by weight forms the basis of the present invention. That is, CPVC with various chlorine contents has been used for pipes, industrial boards, etc., but most of them have a chlorine content of less than 67% by weight. The reason for this is that when the chlorine content exceeds 67% by weight, processability deteriorates (for example, Japanese Patent Publication No. 44-7535). However, the composition of the present invention can be fully extruded, calendared, and injection molded using a conventional processing molding machine for vinyl chloride resins, and can provide a molded article with excellent surface properties. And the chlorine content is 67-71% by weight.
By doing so, it is possible to increase the softening temperature of the molded product, and when the softening temperature according to method B of JIS K 7206 is set to 115°C or higher, the molded product exhibits good hot water resistance against hot water of 90°C or higher. do. In addition, the chlorine content is 71
CPVC in excess of 1% by weight is not preferred because it has poor thermal stability.

In addition, the average degree of polymerization of vinyl chloride resin before chlorination is JI
400-11 as measured by the method of SK 6723
Preferably, it is in the range of 00. If the average degree of polymerization is less than 400, the impact strength of the molded product will be poor, and if it exceeds 1100, the workability will be poor, resulting in a rough surface of the molded product and poor hot water resistance.

The impact resistance reinforcing agent which is component (B) of the present invention is composed of 50 to 70% by weight of a butadiene rubber polymer and 50% by weight of other additives.
It is obtained by graft polymerization of ~30% by weight, and when the graft monomer is styrene-methyl methacrylate type, it is MBS resin, and when it is styrene-acrylonitrile type, it is ABS, resin, styrene-methyl methacrylate-acrylonitrile ternary. If the system is MABS
These are called resins, and these may be used alone or in combination of two or more. The graft polymer suitable for the present invention is a butadiene rubber polymer having an average particle diameter of 100.
In the range of 0 to 5000 angstroms, the composition of the graft part in MBS resin is styrene/methyl methacrylate in an amount of 25 to 80/75 to 20% by weight;
In ABS resin, styrene/acrylonitrile is 2
The ratio of styrene/methyl methacrylate/acrylonitrile is 25-80/20-5015-25% by weight in MABS resins. The average particle size of the butadiene rubber polymer is 1
Outside the range of 000 to 5000 angstroms, the effect of enhancing impact resistance is small; if the composition of the grafted part contains less than 25% styrene, processability deteriorates; and if methyl methacrylate and acrylonitrile are used in too much or too little, the impact resistance is reduced. The strengthening effect is small. The blending amount of component (B) is 5 to 10 parts by weight per 100 parts by weight of CPVC. 5
If it is less than 1 part by weight, the effect of strengthening the impact resistance of the molded product is small;
If it exceeds 0 parts by weight, the hot water resistance of the molded article will deteriorate, which is not preferable. In addition, when chlorinated polyethylene or EVA (ethylene-vinyl acetate copolymer) is used as the impact resistance reinforcing agent, a blister phenomenon occurs and hot water resistance is deteriorated.

The mercaptotin-based heat stabilizer which is component (C) of the present invention is:
It is a well-known substance used for ordinary vinyl chloride-based resins, and its main component is dialkyltin dithioglycolic acid ester with an alkyl group of Cl-08, and a portion of monoalkyltin trithioglycolic acid ester. They may be used alone or in combination of two or more. Ingredient (C)
The blending amount is 1 to 3 parts by weight per 100 parts by weight of CPVC. If it is less than 1 part by weight, the thermal stability of the composition will be insufficient and there is a risk of decomposition during a long run of molding, and if it exceeds 3 parts by weight, the softening temperature of the molded product will be lowered and the hot water resistance will also be deteriorated. Incidentally, it is not preferable to use a lead-based stabilizer or a maleate-based tin stabilizer as a heat stabilizer because when exposed to hot water, the material absorbs water well and tends to cause a blister phenomenon.

Examples of the lubricant which is component (D) of the present invention include polyethylene waxes, hydrocarbon waxes, ester waxes, etc., and these may be used alone or in combination of two or more. These lubricants have a melting point or dropping point of 90
It is preferable that the substance is solid at room temperature above 0.degree. C., and in particular, it needs to be hydrophobic. The amount of component (D) varies depending on the molding method and application, but is set in the range of 1 to 5 parts by weight per 100 parts by weight of CPVC. If it is less than 1 part by weight, the heat generated during processing will be large and the molten material may stick to the metal surface of the processing molding machine. If it exceeds 5 parts by weight, gelation will be insufficient, and the surface properties of the molded product will deteriorate or the strength will decrease. It is easy to run out. -For boat fishing, lead stearate is used as a lubricant.
Although metal soaps such as magnesium stearate, free fatty acids such as stearic acid, or higher alcohols are often used, one of the features of the present invention is that these hydrophilic lubricants are not used.

The inorganic filler which is component (E) of the present invention is Coulter
A filler consisting of fine particles with an average particle size of 400 to 10,000 angstroms as measured by a counter (manufactured by Coulter), and includes surface-treated calcium carbonate, clay, talc, titanium oxide, etc. They may be used alone or in combination of two or more. These substances exist dispersedly in the molded product and have the effect of suppressing the occurrence of blister phenomenon, but an excellent suppressing effect is achieved when the average particle size is within the range of 400 to 10,000 angstroms. Yes, the effect decreases outside this range. The blending amount of component (E) is 0.2 to 1.0 parts by weight per 100 parts by weight of CPVC. If it is less than 0.2 parts by weight, the effect of suppressing the blister phenomenon is small;
If the amount exceeds 1 part by weight, the effect of suppressing the blister phenomenon will be reduced and the physical properties of the molded article will also be affected, which is not preferable.

Although the composition of the present invention contains the above-mentioned components (A) to (E) as essential components, processability improvers, pigments, and other minor additives may be added to this composition as necessary. good. However, among these additives, hydrophilic substances and substances that are easily subject to changes such as hydrolysis by water must be excluded.

One of the characteristics of the composition of the present invention is that the softening temperature of the molded article is 115°C or higher based on the measurement method specified in Method B of JIS K 7206. Therefore, in order to achieve this, Addition of plasticizers, solvents, blowing agents, etc. that would lower the softening temperature must be avoided.

The composition of the present invention can be extrusion molded, calendar molded, or injection molded using ordinary processing and molding machines for vinyl chloride resins, although the resin temperature during processing and molding may vary slightly depending on the processing and molding method. The temperature is preferably in the range of 195 to 230°C.

If the resin temperature during processing and molding is less than 195°C, the surface smoothness of the molded product will be poor and the hot water resistance will be lowered, and if it exceeds 230°C, thermal decomposition will occur, which is undesirable.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these examples.

Example] A vinyl chloride resin with an average degree of polymerization of 700 obtained by a normal suspension polymerization method was suspended in water and chlorinated by blowing chlorine gas under mercury lamp irradiation for 6 hours, and then excess chlorine in the reaction system was removed. After expelling with N2 gas, filter the slurry,
Wash the resin with water and dry it to obtain CP with a chlorine content of 68.7% by weight.
Obtained VC.

CPV with a chlorine content of 6847% by weight thus obtained
The following formulation composition was prepared based on c.

Blended composition: (A) CP V C100 with chlorine content of 68.7% by weight
Weight part (B) MES resin (Product name Yuna Ace B-56
: Manufactured by Kanebuchi Chemical Industry ■) 7〃(C
) di-normal octyltin mercapto stabilizer (trade name TV
S 8831: manufactured by Nitto Kagaku ■) 2 (D) Polyethylene wax-based lubricant (product name ACPE617A manufactured by Nearride Signal Co., Ltd.) 2.5 (E) Ultrafine particle calcium carbonate with an average particle size of 800 angstroms (product name Shiraika CCJi: Shiraishi Kogyo) ■Made by) 0
．． 5 The above blended composition was mixed for 10 minutes with a Henschel type high speed mixer, and then mixed with a test roll at 200°C for 3 minutes.
A sheet with a thickness of 0.7 mm was obtained by kneading for a minute. The sheet surface was smooth. Furthermore, several sheets of this were laminated, and 200
It was molded into a 4 m thick plate using a press at ℃.

From this molded press plate, u60+mn, width 50
+ m test piece was cut out and immersed in 110°C hot water (ion-exchanged water whose temperature was controlled at 110°C in a pressure-resistant container equipped with an electric heater) for 60 days. At the same time, the surface of the test piece was visually observed to check for the presence of blister phenomenon. The results are shown in Table 1.

In addition, a part of the above molded press plate was collected and J
Vikatsu softening temperature is measured based on the measurement method specified in IS K 7206 method B, and furthermore JIS K 711
Charpy impact strength was measured based on the measurement method specified in 1. The results are shown in Table 1.

Example 2 (B) MBS resin of Example 1 (trade name Kane Ace B-5
A blended composition was prepared in the same manner as in Example 1, except that the amount of 6) was increased from 7 parts by weight to 9 parts by weight, and rolled in the same manner to obtain a sheet with a thickness of 0.7++a. The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vikaft softening temperature, and Charpy impact strength were measured. The results are shown in Table 1.

Comparative Example 1 A vinyl chloride resin with an average degree of polymerization of 700 obtained by a normal suspension polymerization method was suspended in water and chlorinated by blowing chlorine gas under mercury lamp irradiation for 3.5 hours to remove excess in the reaction system. After expelling the chlorine with N2 gas, the slurry was filtered, and the resin was washed with water and dried to form a cpv with a chlorine content of 65.2% by weight.
I got c.

Using this CPVC with a chlorine content of 65.2% by weight as a base, a blended composition was prepared in the same manner as in Example 1, and rolled to obtain a sheet with a thickness of 0.7 m.

The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured. The result is the first
Shown in the table.

Comparative Example 2 (B) MBS resin of Example 1 (trade name Kane Ace B-5
A blended composition was prepared in the same manner as in Example 1, except that the amount of 6) was reduced from 7 parts by weight to 3 parts by weight, and a sheet with a thickness of 0.7 mm was obtained by roll processing in the same manner. The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured. The results are shown in Table 1.

Comparative Example 3 (B) MBS resin of Example 1 (trade name Yuna Ace B-5
A blended composition was prepared in the same manner as in Example 1, except that the amount of 6) was increased from 7 parts by weight to 15 parts by weight, and rolled in the same manner to obtain a sheet having a thickness of 0.7 mm. The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured. The results are shown in Table 1.

Comparative Example 4 A blended composition was prepared in the same manner as in Example 1, except that the amount of di-normal octyltin mercapto stabilizer (C) in Example 1 (trade name TVS 8831) was increased from 2 parts by weight to 5 parts by weight. A sheet with a thickness of 0.7 m+ was obtained by preparing and rolling processing in the same manner. The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured.

The results are shown in Table 1.

Comparative Example 5 A blended composition was prepared in the same manner as in Example 1, except that the amount of polyethylene wax-based lubricant (D) in Example 1 (trade name ACPE 617A) was increased from 2.5 parts by weight to 7 parts by weight. Then, roll processing was performed in the same manner to obtain a sheet having a thickness of 0.7 ribs. The surface of the sheet was rough and had holes. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured. The results are shown in Table 1.

Comparative Example 6 Same as Example 1 except that the amount of ultrafine calcium carbonate (trade name: Hakureika CCR) with an average particle diameter of 800 angstroms (E) in Example 1 was increased from 0.5 parts by weight to 2.0 parts by weight. A blended composition was prepared in the same manner and rolled into a sheet having a thickness of 0.7 a+m. The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured. The results are shown in Table 1.

Example 3 Except that the same amount of di-n-butyltin mercapto stabilizer (trade name TVS 1360: manufactured by Nitto Kagaku ■) was used instead of di-n-octyltin mercapto stabilizer (trade name TVS 8831) in Example 1. A blended composition was prepared in the same manner as in Example 1, and rolled in the same manner to a thickness of 0.
A 7 m sheet was obtained. The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured. The results are shown in Table 2.

Example 4 The same procedure as in Example 1 was carried out except that the same amount of stearic acid monoglyceride (trade name Rikemar 5100, manufactured by Riken Vitamin Co., Ltd.) was used instead of (D) polyethylene wax-based lubricant (trade name ACPE 617A) in Example 1. A blended composition was prepared and similarly rolled to a thickness of 0.7 m.
I got a sheet of The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1 to obtain hot water resistance and
Vicat softening temperature and Charpy impact strength were measured. The results are shown in Table 2.

Example 5 Ultrafine calcium carbonate with an average particle size of 6000 angstroms (product name: NCC! 1410: Nitto Funka) was used instead of (E) ultrafine calcium carbonate with an average particle size of 800 angstroms in Example 1 (product name: Hakureika CCR) A blended composition was prepared in the same manner as in Example 1, except that the same amount of Kogyo (manufactured by Kogyo ■) was used, and it was similarly rolled to a thickness of 0.
A sheet of 7+ma was obtained.

The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured. The result is the second
Shown in the table.

Example 6 Titanium oxide (trade name: R650: manufactured by Sakai Chemical Industry Co., Ltd.) with an average particle diameter of 3000 angstroms was used instead of (E) ultrafine calcium carbonate with an average particle diameter of 800 angstroms (trade name: Hakureika CCR) in Example 1. A blended composition was prepared in the same manner as in Example 1 except that the same amount was used,
A sheet having a thickness of 0.7 mm was obtained by roll processing in the same manner. The surface of the sheet was smooth. Furthermore, this sheet was used in Example 1.
It was pressed in the same manner as above and the hot water resistance, Vicant softening temperature and Charpy impact strength were measured. The results are shown in Table 2.

Comparative Example 7 (B) MBS resin of Example 1 (trade name Kane Ace B-5
A blended composition was prepared in the same manner as in Example 1, except that the same amount of chlorinated polyethylene resin (trade name: Daisolac H135, manufactured by Daiso ■) was used instead of 6), and it was rolled in the same manner to obtain a 0-thickness .I got the sheet for 7 cabinets. The surface of the sheet was somewhat rough and holes were observed here and there. Furthermore, this sort was pressed in the same manner as in Example] and the hot water resistance, Vicant softening temperature and Charpy impact strength were measured. The results are shown in Table 2.

Comparative Example 8 Di-n-butyltin maleate stabilizer (trade name: TVS N2oo) was used instead of (C) di-n-octyltin mercapto stabilizer (trade name T~'58831) in Example 1.
Example 1 except that the same amount of OC (manufactured by Nitto Kasei Mai) was used.
A blended composition was prepared in the same manner as above, and rolled in the same manner to obtain a sheet having a thickness of 0.7 m. The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured. The results are shown in Table 2.

Comparative Example 9 Except that the same amount of tribasic lead sulfate (trade name: TL-7000: manufactured by Sakai Chemical Industry ■) was used instead of (C) di-normal octyltin mercapto stabilizer (trade name TV58831) in Example 1. A blended composition was prepared in the same manner as in Example 1, and rolled in the same manner to obtain a sheet having a thickness of 0.7 ttm. The surface of the sheet was rough.

Furthermore, this sheet was pressed in the same manner as in Example 1, and its hot water resistance, Vicat softening temperature, and Charpy impact strength were measured. The results are shown in Table 2.

Comparative Example 10 Ultrafine calcium carbonate having an average particle diameter of 15,000 angstroms (product name: N5ItlOO: Nitto Funka Kogyo Co., Ltd.) was used instead of (E) ultrafine calcium carbonate having an average particle diameter of 800 angstroms (product name: Hakureika CCR) in Example 1. A blended composition was prepared in the same manner as in Example 1, except that the same amount of
I got a sheet of The surface of the sheet was smooth. Furthermore, this sheet was pressed in the same manner as in Example 1 to obtain hot water resistance and
Vicat softening temperature and Charpy impact strength were measured.

The results are shown in Table 2.

As is clear from the results in Tables 1 and 2, the composition of the present invention has a low water absorption of 20 cm/c1i or less, exhibits good hot water resistance without causing any blister phenomenon, and has a smooth sheet surface. It is also a material with excellent properties such as hardness, Vicat softening temperature, and Charpy impact strength.

[Function/Effect] As mentioned above, the resin composition of the present invention provides a molded article with improved hot water resistance, good surface smoothness, and a good balance of heat resistance and impact strength.

Claims (1)

[Claims] 1. A hot water-resistant resin composition characterized by comprising the following components (A) to (E): (A) Post-chlorinated vinyl chloride-based resin with a chlorine content of 67 to 71% by weight 100 parts by weight of resin, (B) 5 to 10 parts by weight of at least one impact reinforcing agent selected from MBS resin, ABS resin and MABS resin, (C) 1 to 3 parts by weight of mercaptotin-based thermal stabilizer, ( D) 1 to 5 parts by weight of a hydrophobic lubricant; (E) 0.2 to 1.0 parts by weight of an inorganic filler having an average particle diameter of 400 to 10,000 angstroms. 2. The hot water-resistant resin composition according to claim 1, wherein the molded article has a softening temperature of 115° C. or higher as measured by the method specified in Method B of JIS K7206. 3. The hot water-resistant resin composition according to claim 1, which has a water absorption amount of 20 mg/cm^2 or less per unit surface area of the molded composition for 60 days in a hot water resistance accelerated test by immersing in hot water at 110°C.