JP3495165B2 - Polyester resin composition with excellent adhesion to silicone rubber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION The present invention relates to durability, and
Strongly combined with silicone rubber with excellent water-decomposability and heat aging resistance
The present invention relates to an adhesive polyester resin composition. In particular,
Akira is applied to the surface of a molded product made of polyester resin composition.
Apply cone rubber to soften polyester resin composition
Cure the silicone rubber at a temperature lower than the temperature,
We adhere to technique to let you join well. [0002] BACKGROUND OF THE INVENTION Thermoplastic polyester resins, especially
Ributylene terephthalate is chemical resistant, heat resistant, mechanical
It has excellent properties and is widely used as an industrial resin. Nearby
Years, the requirements for durability include resistance to hydrolysis and heat aging.
In the field of electric / electronics and automobiles,
Satisfies the required characteristics and has heat resistance, electrical characteristics, and weather resistance
Offering an integrally molded body that is firmly bonded to excellent silicone rubber
A salary is desired. [0003] Conventionally, addition-curable silicone rubber and organic resin
As a method of adhering a molded article of fat, for example,
Apply primer on the surface, and then uncured silicone
There is a known method of curing a material from a resin molded product.
You. [0004] However, using a primer
To remove the molded product from the mold,
A work step of applying a primer is required. Further, a self-adhesive silicone rubber material is formed.
The method of applying and curing the molded resin is to use a mold
When forming an integral molded product with a molded product and silicone rubber
If the silicone rubber itself adheres to the mold,
There is a big difficulty. Furthermore, for synthetic resin moldings
When applying and curing, add self-adhesive silicone
Most rubber materials are polybutylene terephthalate resin
Has sufficient adhesive strength to be used as an integral molded product.
It is not something to do. [0006] SUMMARY OF THE INVENTION The present invention relates to a polybutylene resin.
Demand for industrial resin materials of terephthalate is growing
Significantly improve the hydrolysis resistance and heat aging resistance
Polybutylene terephthalate and silicone rubber
Adhesively bonded with enough adhesive strength to withstand practical use
Integration of terephthalate resin composition and silicone rubber
Obtain molded products, and make molded products simple, reliable, and short.
The purpose is to form an integrally molded product by bonding in time. [0007] Means for Solving the Problems The present inventors have solved the above problems.
As a result of intensive studies to solve the points, the present invention has been reached. That is, the present invention relates to a method of using a titanium compound as a polymerization catalyst.
And low terminal carboxyl group concentration
Mainly composed of phthalate and phenolic antioxidant
Agent and a thioether-based antioxidant,
Compound and / or its polymer,
A molded article of a butylene terephthalate resin composition is obtained,
Apply addition-curable silicone rubber to the surface of the
In the past, the adhesion of addition-curable silicone rubber
Practical use of low or short-time bonding process
With polyester silicone rubber with endurable adhesive strength
This is to obtain a molded product as an integral molded product. Especially injection
The above polybutylene terephthalate resin set using molding method
Adheres to the product under short curing conditions, and
The rubber itself can be released from the mold
Butylene terephthalate resin composition and silicone rubber
The present inventors have found that an integrally molded article can be obtained, and have reached the present invention. That is, the present invention relates to polybutylene terephthalate.
(A) terminal carboxyl groups
When the sill concentration is 15 equivalents / ton or less,
Polybutylene terephthalate using polybutene compound
Per part by weight, (B) at least one silicon source per molecule
A silicon compound having a hydrogen atom directly bonded to a hydrogen atom and / or
Represents 0.05 to 3 parts by weight of the polymer, (C) phenol
0.01 to 0.5 parts by weight of the antioxidant and (D) thioe
Ter antioxidant 0.01 to 0.5 parts by weight
It is a ribethylene terephthalate resin composition. [0010] The polybutylene as the component (A) of the present invention
Lephthalate is terephthalic acid as the main acid component,
1,4-butanediol as the main glycol component
Polyester. Here, “primary” refers to all acids
Occupies at least 80 mol% of the total or total glycol components
That is, it is preferably at least 90 mol%. Of the present invention
Copolymerizable acids in polybutylene terephthalate.
Aromatic dicarboxylic acids other than terephthalic acid are examples
For example, isophthalic acid, naphthalenedicarboxylic acid, diphenyl
Rudicarboxylic acid, diphenyl ether dicarboxylic acid, di
Fexethane dicarboxylic acid, diphenyl ketone dical
Aliphatic dicarboxylic acids such as boric acid and diphenyl sulfone dicarboxylic acid
Carboxylic acids such as succinic acid, adipic acid, sebacic acid
Alicyclic dicarboxylic acids such as cyclohexanedical
Bonic acid, tetralin dicarboxylic acid, decalin dicarboxylic
Acids and the like are exemplified. Copolymerizable glycos other than butanediol
Ethylene glycol hexamethylene glycol
Recall, neopentyl glycol, cyclohexanedi
Methanol, tricyclodecane dimethylol, xylylene
Glycol, bisphenol A, bisphenol B,
Bishydroxyethoxybisphenol A is exemplified.
You. Further, the polyester substantially improves the molding performance.
Compounds having three or more functional groups as long as they are not lost, eg
For example, glycerin, trimethylolpropane, pentaerythri
Thritol, trimellitic acid, trimesic acid, pyromellitic
A citric acid or the like may be copolymerized. The polybutylene used in the present invention
Lephthalate uses a titanium compound as a polymerization catalyst,
The terminal carboxyl group concentration is 15 equivalent / 10⁶g or less
It is necessary. Terminal carboxyl group concentration is 15 equivalents
/ 10⁶g is one of the main effects of the present invention.
No significant improvement in hydrolysis resistance is observed. Also polymerized
When a tin compound is used as a medium, curing of silicone rubber
Is not preferred. Polybutylene terephthalate used in the present invention
The rate is the intrinsic viscosity (orthochlorophenol at 35 ° C)
Value of 0.3 or more
Preferably it is 0.5 or more. The intrinsic viscosity is
If low, the mechanical strength is low and the melt viscosity is low.
It is difficult to use, and there is little meaning to apply the present invention.
is there. The component (B) used in the present invention is less than 1 minute.
At least one silicon-containing compound or polymer thereof
And a SiH group or a vinyl group represented by the following formula (1) or (2)
Is a compound containing [0016] Embedded image (Where m, n, i and j are 1 to 100)
Is an integer. Also, R¹~ R⁷Represents an aliphatic unsaturated bond
It is a substituted or unsubstituted monovalent hydrocarbon that does not contain
Usually, a group having 1 to 10 carbon atoms, preferably hydrogen
Or a group having 1 to 6 carbon atoms. R¹~ R⁷as,
Specifically, for example, hydrogen or a methyl group, an ethyl group,
Alkyl groups such as propyl group and butyl group; for example, phenyl
Aryl such as group, tolyl group, xylyl group and benzyl group
A cycloalkyl group such as a cyclohexyl group;
Part or all of the hydrogen atoms in these groups may be halogen atoms or silicon atoms.
Chloromethyl group, cyano group substituted with a substituent such as an ano group
Examples include ethyl group 3,3,3-trifluoropropyl group
Is done. Note that R¹~ R⁷May be the same or different
No. ) The component (C) used in the present invention,
Nord-based antioxidants are hindered phenol compounds.
You. The phenolic antioxidant is preferably 2,
6-di-tert-butyl-p-cresol, 2,2'-methyl
Len-bis- (4-methyl-6-di-t-butylpheno
4,4'-thiobis (3-methyl-t-butylphen
Nol), 1,1,3-tris (2-methyl-4-hydr)
Roxy-5-t-butylphenyl) butane, pentaerythri
Sthyl-tetrakis [3- (3,5-di-t-butyl)
-4-hydroxyphenyl) propionate], octa
Decyl-3- (3,5-di-tert-butyl-4-hydroxy)
(Phenyl) propionate, and particularly preferably,
Pentaerythrityl-tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propione
G]. One or two phenolic antioxidants
The above can be used simultaneously. Phenolic antioxidants
The compounding amount of polybutylene terephthalate resin is 100
0.01 to 0.5 parts by weight based on parts by weight
And 0.1 to 1.3 parts by weight is preferred. 0.01 weight
When the amount is less than 0.1 part, the effect of improving heat resistance is small, and
Even if it is more than 5 parts by weight, the effect of improving heat aging resistance is expected.
I can't. The thio which is the component (D) used in the present invention
The ether antioxidant is preferably ditridecyl-chi.
Odipropionate, tetrakis [methylene-3-
(Dodecylthio) propionate], bis [2-methyl]
―4- ｛3-n-alkyl (C ₁₂Or C₁₄) Thioprop
Onyloxy {-5-t-butylphenyl] sulfide
It is. The amount of the thioether-based antioxidant is
0.0 parts per 100 parts by weight of butylene terephthalate resin
1 to 0.5 parts by weight, and 0.1 to 0.5 parts by weight.
0.3 parts by weight is preferred. If less than 0.01 parts by weight
In this case, the effect of improving heat resistance cannot be expected. Also, a general phosphorus antiacid as an antioxidant
Agents should be used to inhibit the curing of silicone rubber.
It is not. The polybutylene terephthalate resin of the present invention
The composition may further include a reinforcing material such as glass fiber, an inorganic filler.
Materials, pigments, flame retardants, flame retardant aids, nucleating agents, and light stabilizers.
Can be combined. The polybutylene terephthalate resin of the present invention
Addition-curable silicone for improving the adhesiveness of the composition
A rubber composition is a catalyst containing a platinum compound and containing a vinyl group.
Organopolysiloxane and organohydrogenpo
It is cured by the addition reaction of siloxane. The vinyl group-containing organopolysiloxane is
At least two vinyl groups bonded to a silicon atom in one molecule
I have The vinyl group-containing organopolysilo
The molecular structure of a xan is straight or branched.
And the vinyl group exists only at the terminal of the molecule.
Even if it exists only in the middle of the molecular chain,
It may be present at the end and in the middle of the molecular chain. In particular,
It can be represented as the general formula (2). [0027] Embedded imageThe vinyl-containing organopolysiloxane is
Viscosity at 25 ° C is 10 to 1,000,000 cSt
(Centistokes), and 1
Preferably, it is between 00 and 10,000 cSt.
Incidentally, the vinyl group-containing organopolysiloxane itself is
It can be manufactured by a known method. Also, an organohydrogenpolysiloxy
Sun states that only one hydrogen atom in a molecule is bonded to a silicon atom.
It has at least two. This component acts as a crosslinker
The composition of the present invention uses the silicon atom
The bonded hydrogen atom and the vinyl group-containing polysiloxane
It is cured by an addition reaction with vinyl groups.
You. This organohydrogenpolysiloxane is
The molecular structure of the compound is not particularly limited, and may be linear, branched, or cyclic.
Any structure such as a shape can be used. Also,
Of organohydrogenpolysiloxane at 25 ° C
Is usually 0.5 to 1000 cSt.
More preferably, it is 1 to 200 cSt. The organohydrogenpolysiloxane
Is, for example, the following average composition formula: [0032] Embedded image H_a(R⁸)_bSiO_{(4-ab) / 2} (Where R⁸Is a substitution not containing an aliphatic unsaturated bond, or
An unsubstituted monovalent hydrocarbon group, wherein a and b are 0 <a <
2, 1 ≦ b ≦ 2 and 2 ≦ a + b ≦ 3
You. ) Are suitably used. In the above average composition formula, R⁸Fatty unsaturated bond
A substituted or unsubstituted monovalent hydrocarbon group containing no
And usually a group having 1 to 10 carbon atoms, preferably
1 to 7 groups. R⁸Specifically, the above 1
The groups exemplified as to 7 are similarly exemplified. A and b are respectively 0 <a <2,
1 ≦ b ≦ 2, 2 ≦ a + b ≦ 3, preferably
Or 0.3 ≦ a ≦ 1 and 2 ≦ a + b ≦ 2.7
Is a number. The component organohydrogenpolysiloxy
Sun can be manufactured in a manner known per se,
Always, R⁸SiHCl_Two, R⁸ _ThreeSiCl, R⁸ _TwoSiC
l_Two, R⁸ _TwoHydrolyzes chlorosilanes such as SiHCl
Or the siloki obtained by such hydrolysis.
It can be produced by equilibrating the sun. An organohydrogenpolysiloxane and
Specifically, specifically, a compound represented by the following formula is exemplified.
Can be [0037] Embedded imageThe organohydrogenpolysiloxane
The blending amount is not particularly limited, but the vinyl group-containing
Viable bonds to silicon atoms contained in luganopolysiloxane
Organohydrogenpolysiloxy for one nil group
1 to 5 hydrogen atoms bonded to the silicon atom of sun
It is preferable to mix the amounts. A platinum compound as an addition reaction catalyst is a vinyl compound.
Group and organohydrogenpolysiloxane silicon source
To promote the addition reaction with the hydrogen atom bonded to the
What is used. As the platinum compound, usually, an organo
Used as an addition reaction catalyst for polysiloxane compositions
Can be used. Specifically,
Platinum and, for example, H_TwoPtCl₆・ XH_TwoO, NaH
PtCl₆・ XH_TwoO, KHPtCl₆・ XH_TwoO, N
a_TwoPtCl₆・ XH_TwoO, K_TwoPtCl₆・ XH
_TwoO, PtCl_Four・ XH_TwoO, PtCl_Two, Na_TwoPt
Cl_Four・ XH_TwoO, H_TwoPtCl_Four・ XH_TwoO (here
Where X is a positive integer. ) Etc.
You. Further, the platinum compound and, for example, hydrocarbons,
Using complex with coal, vinyl group-containing cyclic siloxane, etc.
You can also. The compounding amount of the platinum compound is
Ganopolysiloxane and organohydrogenpolysilo
Any amount is sufficient to promote the addition reaction with xan.
Usually, 0.1 to 100 ppm in terms of platinum metal
Desirably. This silicone rubber composition is used in practical applications.
In addition to the above-mentioned components,
Various additives can be compounded if necessary
You. For example, methylphenyl silicone as a lubricant
SiO to enhance the strength of oils and cured products_Twounit,
(CH_Two= CH) R '_TwoSiO_0.5And R '_TwoSiO
_0.5Unit (wherein R 'does not contain an aliphatic unsaturated bond)
Monovalent hydrocarbon group. ) Resin structure
Ganopolysiloxane (JP-B-38-37771, JP-B)
No. 45-9476).
Even when these are blended, they are still included in the composition
One vinyl group bonded to all silicon atoms
It is necessary to have 1 to 5 hydrogen atoms bonded to an element atom.
is there. Further, heat recovery during curing of silicone rubber
Decrease in shrinkage, decrease in coefficient of thermal expansion of the elastic body obtained by curing,
Thermal stability, weather resistance, chemical resistance, flame retardancy, mechanical strength, etc.
Filler is added for the purpose of improving gas permeability and reducing gas permeability
You may. Such fillers include, for example,
Silica, quartz powder, glass fiber, carbon black
H; For example, metallization of alumina, iron oxide, titanium oxide, etc.
Compounds; for example, calcium carbonate, magnesium carbonate
Such as metal carbonates, suitable pigments as needed,
Dyes, antioxidants and the like can be added. filler
Is usually per 100 parts by weight of the organopolysiloxane,
5 to 200 parts by weight are blended. The polybutylene terephthalate resin of the present invention
The composition is a two-component addition-curable silicone rubber (vinyl-based)
A mixture of a containing organopolysiloxane and a platinum catalyst,
Separately packaged with organohydrogenpolysiloxane
And then mix them at the time of use)
Good adhesion to the object becomes possible. [0045] EXAMPLES The present invention will be specifically described below with reference to examples.
I do. In the examples, “parts” means “parts by weight”. Po
The intrinsic viscosity [η] of the limmer is 3 in orthochlorophenol.
It is a value calculated from the solution viscosity measured at 5 ° C. Further, the terminal carboxyl group concentration (COO
H) is the method of A. Conix
｛(Makromol. Chem, Vol-26, 22
6 (1958)}⁶g
The number of equivalents. [Examples 1 to 3, Comparative Examples 1 to 6] Polymerization catalyst
Polybut using tetrabutoxyside titanate
130 of Tylene terephthalate (intrinsic viscosity: 0.90)
C. x 5 hours, and methyl-
Drogen silicone oil (Toray Dow): trade name S
H1107), Pentaery as a phenolic antioxidant
Sthyl-tetrakis [3- (3,5-di-t-butyl)
-4-Hydroxyphenyl) propionate], thioe
-Tetrakis [methylene-3-] as a telluride antioxidant
(Dodecylthio) propionate], as shown in Table 1.
In a V-type blender. The resulting blend
The mixture was heated to a barrel temperature of 250 ° C using a 44 mm twin screw extruder.
Melt and knead to cool and cut the thread discharged from the die.
This was cut to obtain molding pellets. Then, the pellets were heated at 130 ° C. for 5 hours.
After drying, a 5 oz.
Cylinder temperature 260 ° C, mold temperature 4
0 ° C, injection pressure 700kg / cm^Two, Cooling time 20 seconds
Test specimens (AS
TM4) and an adhesive test piece. Hydrolysis resistance
Test is performed at 122 ° C and 100% relative humidity for 60 hours.
Tensile strength and rupture of specimens subjected to wet heat treatment
This was done by measuring the elongation. Heat resistance test
Specimen heat-treated at 170 ° C for 500 hours
By measuring tensile strength and elongation at break
Was. Preparation of addition type silicone rubber: in one molecule
It has two methylvinylsiloxane units,
Dimethylpolysiloxy terminated with ruvinylsiloxy group
Sun (viscosity at 25 ° C: 1000 cSt) 100 weight
Parts by weight, the amount of hydrogen atoms bonded to silicon atoms per 100 g
0.739 moles of methyl hydrate median polysiloxy
4.6 parts by weight of sun, converted from chloroplatinic acid to octyl alcohol
0.12 parts by weight of a neutral solution (platinum content: 0.5%)
did. Further, the above polybutylene terephthalate resin
Figure 1 shows the adhesion test between the composition and the addition-curable silicone rubber.
25mm width x 15mm length x thickness
Apply 0.2mm and heat at 130 ° C for 1 minute to harden
Polybutylene terephthalate resin composition and silicone
Adhesive strength between silicone rubber and chrome
The peelability between the bonded test piece and the same size metal jig.
Was evaluated. [0052] [Table 1]As shown in Table 1, terminal carboxyl group concentration
Is 35 equivalents / ton of polybutylene terephthalate resin
Is poor in hydrolysis resistance as shown by the results of PCT.
10 terminal equivalent / 10⁶g poly
Butylene terephthalate resin can show good results
I understand. Further, regarding the heat aging property, phenol-based
Combining antioxidants with thioether antioxidants
By this, it is greatly improved. Further, a polybutylene terephthalate resin set
Compounded with methyl hydrogen silicone oil
Then, the polybutylene terephthalate molded product and silicon
Rubber and rubber are strongly adhered and metal is easy to peel off
It has become possible to obtain such favorable results. Example 4, Comparative Examples 7 and 8 Same as Example 1.
Compositions with the proportions shown in Table 2 in a similar manner
The same evaluation was performed. As a result, a polybutylene catalyst using a tin compound as a catalyst was obtained.
Add lentephthalate resin and phosphorus antioxidant
If the silicone rubber does not work,
I knew it wasn't. The results are shown in Table 2. [0058] [Table 2]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an elevational view showing a state in which silicone rubber is sandwiched between two molded articles made of a polybutylene terephthalate resin composition or a metal of the present invention, and the two molded articles are bonded to each other. FIG. FIG. 2 is a top (plan) view of the state of FIG. 1; [Description of Signs] Reference numeral 10 denotes a contact portion of the surface of the two molded products. Reference numeral 12 denotes a molded article of polybutylene terephthalate resin. 14
Indicates a metal molded product. Reference numeral 20 denotes a silicone rubber interposed in a contact portion.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 67/02

Claims (1)

(57) [Claims 1] (A) When the terminal carboxyl concentration is 15 equivalents / 10 ⁶ g or less, and based on 100 parts by weight of polybutylene terephthalate containing a titanium compound as a polymerization catalyst residue,
(B) 0.05 to 3 parts by weight of a silicon compound having a hydrogen atom directly bonded to at least one silicon atom in one molecule and / or a polymer thereof, (C) phenolic antioxidant 0.01 to A polybutylene terephthalate resin composition having excellent adhesion to silicone rubber, which comprises 0.5 part by weight and 0.01 to 0.5 part by weight of a (D) thioether-based antioxidant.