JPH09241914A - Shock-resistant human body protector - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a shock-resistant human body protector, for example, a helmet which is improved in fluidity and resistance at cold temperature and satisfies the ductile fracture characteristics at cold temperature by introducing blocks of a polyorganosiloxane into an aromatic polycarbonate resin. SOLUTION: A resin molding is obtaines by using singly an aromatic polycarbonate resin containing polyorganosiloxane blocks or a mixture thereof with an aromatic polycarbonate containing no polyorganosiloxane block. The content of polyorganosiloxane in the resin is usually 0.1-10wt.%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an impact-resistant human body protector, and more particularly to an aromatic polycarbonate resin containing a block of polyorganosiloxane or a mixture of the resin and an aromatic polycarbonate resin containing no block of polyorganosiloxane. The present invention relates to a human body protector using a resin molded body made of.

[0002]

2. Description of the Related Art Polycarbonate resins have been used for various human body protectors because they have high strength, high heat resistance, high impact resistance and transparency. Among them, the following is a review of the prior art regarding the suitability of the polycarbonate resin used as a material for a typical helmet and the problems in its use.

Japanese Unexamined Patent Publication No. 53-104346 discloses a helmet in which an outer portion of a three-layer structure including an adhesive layer is formed of a thermoplastic resin such as polycarbonate, and Japanese Unexamined Patent Publication No. 53-134545 discloses an outer helmet. A helmet formed of a shell, an inner shell, and a transparent eaves, in which the outer shell and the transparent eaves are molded with a polycarbonate resin, is disclosed. JP-A-58-156008 discloses a cap body molded with a polycarbonate resin. Japanese Patent Application Laid-Open No. 58-163709 discloses a helmet in which a cap body formed of a polycarbonate resin has a surface coated with a top coat.
Japanese Patent Publication No. 96046 discloses a helmet in which a hat-shaped main body is formed of a transparent polycarbonate resin and only the frontal part is made transparent, and the back of the head is coated with a light-shielding paint.

That is, it is disclosed that the polycarbonate resin can be used as a main material for the outer portion of the helmet and the transparent eaves portion. However, in order to satisfy the ductile fracture characteristics at a low temperature required for the material forming the outer shell of the helmet, it is necessary to use a polycarbonate resin having poor fluidity, that is, poor moldability. Therefore, an improved resin having good fluidity and good low temperature impact resistance is desired for helmets and the like.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an impact resistant human body protector such as a helmet using a polycarbonate modified resin having good fluidity and low temperature impact resistance from the above viewpoint. To do.

[0006]

In order to solve the above problems, the inventors of the present invention have conducted extensive studies and, as a result, introduced a polyorganosiloxane block into an aromatic polycarbonate resin to provide a human body having the desired performance. It was found that a protective equipment can be obtained, and the present invention was completed based on this finding.

That is, the gist of the present invention is as follows. (1) A resin molded product made of an aromatic polycarbonate resin (A) containing a polyorganosiloxane block or a mixture of the resin (A) and an aromatic polycarbonate resin (B) not containing a polyorganosiloxane block was used. Impact resistant personal protective equipment. (2) The impact-resistant human body protector according to claim 1, wherein the content of the polyorganosiloxane in the resin forming the molded body is 0.1 to 10% by weight. (3) The impact-resistant human body protector according to (1) or (2) above, wherein the repeating unit of polyorganosiloxane is represented by formula (I).

[0008]

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[R ^a and R ^b are an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. (4) The shock-resistant human body protector according to any one of (1) to (3) above, wherein the shock-resistant human body protector is a helmet.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the contents of the present invention will be described in detail. (1) Aromatic polycarbonate resin containing a polyorganosiloxane block An aromatic polycarbonate resin containing a polyorganosiloxane block typically contains the above-mentioned repeating unit (I), and more specifically, Examples are polyorganosiloxanes of the formula (II) and (III
) A block copolymer with an aromatic polycarbonate comprising a repeating unit represented by the formula:

[0011]

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[R ^{1 to} R ⁴ are alkyl groups having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, etc.) or carbon number 6-20, preferably 6-18 aryl groups (eg phenyl, tolyl, xylyl,
Naphthyl group, etc.), which may be the same or different. A is a divalent organic residue containing an aliphatic or aromatic group, such as a methylene group, an ethylene group, a propylene group, a butylene group, a penteline group, a hexylene group, an ethylidene group, an isopropylidene group, a cyclopentylene group, a cyclohexylene group. , Cyclopentylidene group, cyclohexylidene group, o-allylphenol residue, p
-Vinylphenol residue, eugenol residue, bisphenol A residue and the like. n is 1 to 500. ]

[0013]

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[R ⁵ and R ⁶ are halogen atoms (chlorine atom, bromine atom, fluorine atom, iodine atom) alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, n-
(Butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, etc.) or C6-20, preferably 6-1
8 aryl groups (eg, phenyl group, tolyl group, xylyl group, naphthyl group, etc.), which may be the same or different. p and q are 0-4. Z is a single bond, an alkylene group or an alkylidene group having 1 to 20 carbon atoms, preferably 2 to 18 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, penterylene group, hexylene group, ethylidene group, isopropylidene group, etc.) , A cycloalkylene group or a cycloalkylidene group having 5 to 20 carbon atoms (for example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group, etc.), an alkylene ester group, an alkylenecarbonyl group, -O-,- S -, - SO ₂ -, or -CO
-Indicates a bond represented by a bond. m is 1 to 150. ]

For the block copolymer, the above formula (II), (II
When the repeating unit of the formula (I) is represented by II and III, there are III-II-III type, III-II type, II-III-II type, multiblock type and the like, but any of them may be used. Especially,
Type III-II-III, which has a simple production process, can be preferably used. Since high impact resistance is required, it is preferable that the number n of repeating siloxane units is large, but if it is 500 or more, it becomes difficult to produce a copolymer. Preferably 10
It is 450, more preferably 20 to 400. Note that n
When it exceeds 60, it becomes cloudy, but when it is 60 or less, it becomes transparent. Therefore, the range of 1 to 60, preferably 10 to 50 is suitable for molding a shock resistant human body protector such as a transparent helmet. .

Aromatic polycarbonate-polyorganosiloxane block copolymer of the present invention (III-II type above)
Is described in JP-A-7-292113 by the present applicant. Specifically, the polycarbonate oligomer and the one-end-blocked polyorganosiloxane are separately produced, and the organic solvent is used in an amount of 0.12 to 35 parts by weight of the one-end-blocked polyorganosiloxane with respect to 100 parts by weight of the polycarbonate oligomer. And an aqueous solution of an alkali metal hydroxide of a dihydric phenol and a terminal stopper of a monohydric phenol. Further, a tertiary amine or a quaternary ammonium salt usually used as a catalyst in the production of polycarbonate is added. By performing an interfacial polycondensation reaction using such a catalyst, a polycarbonate-polyorganosiloxane block copolymer can be obtained.

As a typical method for producing a polyorganosiloxane having one end blocked, a haloformate group represented by the general formula (V) is used per 1 mol of the polyorganosiloxane having both ends reactive represented by the following formula (IV). Alternatively, by reacting a compound having a carboxylic acid halide group or the like, that is, a modifying agent in an amount of 0.1 mol or more and less than 2 mol, the modified polyorganosiloxane having one end blocked represented by the formula (VI) can be produced. .

[0018]

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[R ^{1 to} R ⁴ and A are the same as those in the above formula (II). ]

[0020]

[Chemical 6]

[X is a halogen atom, D is a single bond or -O
-Indicating binding. R ⁷ represents a group represented by an alkyl group having 1 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms. ]

[0022]

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[R ^{1 to} R ⁴ and A are the same as those in the above formula (II), and D and R ⁷ are the same as those in the above formula (V). As a typical method for producing a polycarbonate oligomer, a dihydric phenol 10 represented by the following general formula (VII) is used.
A polycarbonate oligomer having formula (III) obtained by mixing and optionally reacting a catalyst such as triethylamine in a solvent such as methylene chloride at a ratio of 110 to 150 moles of phosgene to 0 moles is obtained. be able to.

[0024]

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[R ⁵ , R ⁶ , Z, p and q are defined by the above formula (III
Is the same as). Usually, in the production of a copolymer, a homopolymer of a polycarbonate is also produced, which is substantially a mixture of the copolymer and the homopolycarbonate. In the present invention, this is referred to as an “aromatic containing a block of polyorganosiloxane. It is referred to as "polycarbonate resin" or simply "copolymer".

Other aromatic polycarbonate resins containing polyorganosiloxane blocks include graft copolymers in which polysiloxane repeating units are graft polymerized. Its typical polymer structure is composed of a polysiloxane moiety represented by the formula (VIII) and a main repeating unit represented by the formula (III).

[0027]

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[R ⁵ , R ⁶ , p and q are the same as those in the above formula (III). Z is an alkylene group, an alkylene ester group or an alkylenecarbonyl group among those shown in the above formula (III). ^{R 8, R 9, R 10} , R 11, R 12 is an alkyl group or an aryl group. k is 0 to 1000
It is. Specifically, the polysiloxane group is polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane, or the like. The dihydric phenol having an unsaturated group that reacts with polysiloxane is 4
-Methyl-2,4-bis (4-hydroxyphenyl)-
1-pentene, 4-methyl-2,4-bis (4-hydroxyphenyl) -2-pentene, 4,4'-bis (4-
Hydroxyphenyl) -1-pentene, 4,4′-dihydroxychalcone, 2,2′-bis (4-hydroxyphenyl) -2-acryloyltan, 1,3-bis (4-
Hydroxyphenyl) -2-buten-1-one.

[0029]

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[R ⁵ , R ⁶ , Z, p, q and m are the same as in the above formula (III). The graft copolymer is disclosed in JP-A-7-16589.
No. 7 is described. (2) Aromatic Polycarbonate Resin Not Containing Polyorganosiloxane Block In the present invention, in the copolymer of (1) above, a homopolymer of aromatic polycarbonate, that is, an aromatic not containing a polyorganosiloxane block, is added to the copolymer according to need. Group polycarbonates can be mixed and used.

This aromatic polycarbonate usually has the same repeating unit as that of the above formula (III).
It can be easily produced by reacting a polyhydric phenol with a phosgene or a carbonate compound by a known method such as an interfacial polymerization method, and there is no particular limitation on raw materials, production methods and the like. Examples of dihydric phenols include hydroquinone, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl)
Alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenylsulfone, bis (4-hydroxyphenyl) ketone, 9,9 2, bis (4-hydroxyphenyl) propane (bisphenol A) is suitable among them, and biscarbonate compounds such as diphenyl carbonate are preferred. Dialkyl carbonates such as diaryl carbonate, dimethyl carbonate and dimethyl carbonate.

The terminal terminator may have any structure as long as it is a monohydric phenol, and is not particularly limited. For example, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, phenol, p-
tert-amylphenol, p-nonylphenol, p-cresol, tribromophenol, p-bromophenol,
4-hydroxybenzophenone and the like, which may be used alone or in combination of two or more.

Further, a branching agent may be used in combination as long as the effects of the present invention are not impaired. 1,1,1-Tris as branching agent
(4-hydroxyphenyl) ethane, α, α ', α''-tris
(4-Hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [α-methyl-α- (4'hydroxyphenyl) ethyl] -4- [α ', α'-bis (4''- Compounds having three or more functional groups such as hydroxyphenyl) ethyl] benzenephloroglucin, trimellitic acid, and isatinbis (o-cresol) are suitable. (3) Resin composition A kneading method comprising the aromatic polycarbonate resin containing the polyorganosiloxane block of the above (1) or a mixture of the resin (1) and an aromatic polycarbonate resin (2) containing no polyorganosiloxane block. It does not matter whether it is blended by machine or dry blended. The polyorganosiloxane content in the resin composition is usually 0.1 to 1, including the case where the above mixture is used.
It is 10% by weight, preferably 0.5 to 8% by weight, more preferably 1 to 6% by weight. If the polyorganosiloxane content is less than 0.1% by weight, the impact resistance will decrease. If it exceeds 10% by weight, heat resistance and rigidity will be reduced.

The viscosity average molecular weight (Mv) of the resin composition is usually 15,000 to 26000, preferably 170.
It is from 0 to 25,000, and more preferably from 18,000.
It is 24,000. Viscosity average molecular weight (Mv) is 1500
If it is less than 0, the impact resistance tends to be lowered. If it exceeds 26000, the fluidity tends to be lowered. Further, various additives such as an antioxidant, a release agent, a weathering agent, an anti-UV agent, a colorant and the like may be added within a range that does not impair the effects of the present invention. (4) Impact-resistant human body protector The impact-resistant human body protector of the present invention is an article having a function of protecting a human body against an external impact, and specifically, a helmet, protective glasses, and a baseball catcher.・ There are protectors for ice hockey players and American football players, and kendo armor. For example, the outer shell of the helmet can be molded by injection molding or the like with the above resin composition, and the inner shell of the helmet can be made by combining known buffers of several types or a net with integrated chin straps. The helmet that can be used is not particularly limited, and can be used as a motorcycle helmet, a safety helmet, a baseball helmet, and the like.

[0035]

The present invention will be further described in detail with reference to production examples, examples and comparative examples. Production Example 1 Production of aromatic polycarbonate (PC) oligomer 60 k in 400 liter of 5% sodium hydroxide aqueous solution
g of bisphenol A was dissolved to prepare an aqueous solution of bisphenol A in sodium hydroxide. Then, this sodium hydroxide aqueous solution of bisphenol A kept at room temperature was introduced at a flow rate of 138 liters / hour and methylene chloride at a flow rate of 69 liters / hour through an orifice plate into a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m. Then, phosgene was co-currently flown thereinto and blown at a flow rate of 10.7 kg / hour to continuously react for 3 hours.

The tubular reactor used here was a double tube, and cooling water was passed through the jacket to keep the reaction solution discharge temperature at 25 ° C. The pH of the discharged liquid is 10 to 1
1 was prepared. The reaction solution thus obtained is allowed to stand, whereby the aqueous phase is separated and removed, and the methylene chloride phase (220 liters) is collected.
An oligomer (concentration: 317 g / liter) was obtained. The degree of polymerization of PC oligomer obtained here is 2 to 4, the concentration of chloroformate group was _0. 7N.

Production Example 2-1 Synthesis of Reactive Polydimethylsiloxane (PDMS) -A 1483 g of octamethylcyclotetrasiloxane, 9
6 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed and stirred at room temperature for 17 hours. Then the oil phase is separated and 25 g of sodium hydrogen carbonate is added to 1
Stirred for hours. It was filtered and vacuum distilled at 150 ° C. and 3 torr to remove low boilers.

[0038] and 60g of 2-allylphenol _0.001
To a mixture with 4 g of platinum chloride-platinum as an alcoholate complex was added 294 g of the oil obtained above at 90 ° C.
Was added at the temperature of. The mixture was stirred for 3 hours while maintaining the temperature of 90 to 115 ° C. The product was extracted with methylene chloride and washed 3 times with 80% aqueous methanol to remove excess
2-Allylphenol was removed. The product was dried over anhydrous sodium sulphate and evaporated in vacuo to a temperature of 115 ° C.

The obtained terminal phenol PDMS is NMR
The number of repeating dimethylsilanooxy units was 30 by the measurement. Preparation Example 2-2 Synthesis of Reactive PDMS-B Same as Preparation Example 2-1 except that the amount of 1,1,3,3-tetramethyldisiloxane was changed to 33.5 g in Preparation Example 2-1. Operated.

The obtained terminal phenol PDMS is NMR
The number of repeating dimethylsilanooxy units was 80. Production Example 2-3 Synthesis of Reactive PDMS-C Same as Production Example 2-1 except that the amount of 1,1,3,3-tetramethyldisiloxane in Production Example 2-1 was changed to 18.1 g. Operated.

The obtained terminal phenol PDMS is NMR
The number of repeating dimethylsilanooxy units was 150. Production Example 3-1 Production of PC-PDMS Copolymer A 185 g of reactive PDMS-A obtained in Production Example 2-1 was dissolved in 2 liters of methylene chloride and mixed with 10 liters of PC oligomer obtained in Production Example 2. A solution prepared by dissolving 26 g of sodium hydroxide in 1 liter of water and 5.7 cc of triethylamine were added thereto, and the mixture was stirred at 500 rpm for 1 hour at room temperature.

Thereafter, bisphenol A600 was dissolved in 5 liters of a 5.2 wt% sodium hydroxide aqueous solution, 8 liters of methylene chloride and p-ter.
81 g of t-butylphenol was added, and the mixture was stirred at 500 rpm for 1 hour at room temperature. After that, add 5 liters of methylene chloride, wash with 5 liters of water, and wash with 0.0
Alkali washing with 5 liters of 2N aqueous sodium hydroxide solution, acid washing with 5 liters of 0.2N hydrochloric acid and water washing with 5 liters of water are carried out in order, and finally methylene chloride is removed to obtain a chip-like PC-PDMS copolymer. Obtained.

Production Example 3-2 PC-PDMS Copolymer B
Production of Production Example 3-1, In place of the reactive PDMS-A 185 g, reactive PDMS-B 380 g, p-tert-butylphenol 81 g, p-cumylphenol 114 g.
The same procedure as in Production Example 3-1 was carried out except that the above was changed to.

Production Example 3-3 PC-PDMS Copolymer C
Production of Reactive PDMS-A in Production Example 3-1
DMS-C, p-tert-butylphenol 83g
Was changed to 129 g of p-cumylphenol, and the same as in Production Example 3-1. Table 1 shows the viscosity-average molecular weight (Mv), PDMS content and transparency of the obtained PC-PDMS copolymers-A to C.

[0045]

[Table 1]

Production Examples 4-1 to 4 The obtained copolymer and aromatic polycarbonate resin are shown in Table 2.
Dry blending was carried out in the proportions shown in, and the mixture was extruded at 280 ° C and pelletized. In Production Examples 4-1 and 4-3, 20% of tris (nonylphenyl) phosphite was used as an antioxidant.
0 ppm was added. Mv and PDM of the obtained pellet
The S content was measured. Table 2 shows the results. As a polycarbonate resin, Teflon F manufactured by Idemitsu Petrochemical Co., Ltd.
N1900A (Mv: 19400) and FN1700A
(Mv: 17700) was used.

[0047]

[Table 2]

The obtained pellets were molded at 300 ° C. and the Izod impact strength was measured. The results are shown in Table 3. For reference, polycarbonate resin Tufflon A2500 (Mv: 23500), A1 manufactured by Idemitsu Petrochemical Co., Ltd.
900 (Mv: 19400) and A1700 (Mv: 1)
7700) Izod impact strength is also shown in Table 3.

[0049]

[Table 3]

Production Examples 4-1 to 4 and A25 obtained this time
00 is completely ductile fracture up to -30 ° C and is suitable as a material for helmets, but A1900 and A170
0 is brittle fracture and is not suitable. Examples 1 to 4 and Comparative Example 1 Production Examples 4-1 to 4 suitable as materials for helmets
And A2500, helmets were molded. Toshiba Machine Co., Ltd. IS-350FA3 was used as the molding machine, the product mold shape had an average wall pressure of 2.5 mm, and the gate shape had a diameter of 6 mm.
A mm direct gate was used. Product weight is 290
g. The results are shown in Table 4.

[0051]

[Table 4]

15% in Examples 1 to 3, 2 in Example 4
1% molding cycle can be shortened. Production Examples 5-1 to 4 PC-PDMS copolymer A was used as the PC-PDMS copolymer, and polycarbonate resin Teflon FN1900A (Mv: 19400) from Idemitsu Petrochemical Co., Ltd. was used as the polycarbonate resin.
And FN3000A (Mv: 30,000) as a white content, titanium dioxide [CR-made by Ishihara Sangyo Co., Ltd.
63 (titanium dioxide surface-treated with 1% silica / alumina and 0.5% dimethyl silicone)],
Organopolysiloxane (Toray. Dow Corning Silicone BY
16-160), as an antioxidant, tris (2,4-di-te
rt-Butylphenyl) phosphite was used, compounded in the proportions shown in Table 5, extruded at 280 ° C., and pelletized.
Table 5 also shows the Mv and PDMS content of the obtained pellets.

[0053]

[Table 5]

Examples 5-7, Comparative Example 2 Using the pellets obtained in Production Examples 5-1-4, an industrial safety hat having an average wall thickness of 3.2 mm was molded at 300 ° C. The obtained industrial safety hat was subjected to an impact absorption test described in JIS T 8131. Table 6 shows the results. The test was conducted at high temperature (50 ° C) and low temperature (-10 ° C), 5 each.
All of the five pieces conformed to the standard and were regarded as "passed".

[0055]

[Table 6]

[0056]

According to the present invention, it is possible to achieve a shortening of the molding cycle while exhibiting ductile fracture at low temperature. I also made a good and transparent helmet. Good as an impact resistant human body protection.

Claims (4)

[Claims] 1. A resin molded product comprising an aromatic polycarbonate resin (A) containing a polyorganosiloxane block or a mixture of the resin (A) and an aromatic polycarbonate resin (B) not containing a polyorganosiloxane block. Impact resistant personal protective equipment used. 2. The content of the polyorganosiloxane in the resin constituting the molded body is 0.1 to 10% by weight.
Impact-resistant personal protective equipment described in. 3. The impact-resistant human body protector according to claim 1, wherein the repeating unit of the polyorganosiloxane is represented by the formula (I). Embedded image [R ^a and R ^b are alkyl groups having 1 to 6 carbon atoms or phenyl groups, and may be the same or different. ] 4. The impact resistant human body protector according to claim 1, wherein the impact resistant human body protector is a helmet.