JPH03163182A - Adhesive - Google Patents

Abstract

PURPOSE:To obtain an adhesive excellent in heat resistance, weathering resistance, chemical resistance and transparency and having a high adhesive strength by using a polymeric substance prepared by dissolving a fluorohydrocarbon polymer in an acrylic monomer, polymerizing the solution and optionally further converting the polymer into an IPN. CONSTITUTION:An adhesive containing a polymeric substance obtained by dissolving an acrylic monomer-soluble fluorohydrocarbon polymer in an acrylic monomer, polymerizing the solution and optionally further converting the polymer into an IPN. As the fluorohydrocarbon polymer, one soluble in an acrylic monomer can be used, and a vinylidene fluoride copolymer is exemplified. The vinylidene fluoride copolymer is desirably one having a number-average mol.wt. of 500-1000000, and its content is desirably 10-60wt.%. As the acrylic monomers, methyl methacrylate and fluorinated acrylic monomer are desirable.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to an adhesive having excellent welding strength.

(Prior art) As an adhesive for fluororubber, Jubei epoxy adhesive adhesive is widely used as adhesive adhesive with excellent adhesive strength. The current situation is that it peels off over time, so it's a bit of a pain.

(Problems to be Solved by the Invention) The object of the present invention is to provide excellent heat resistance, weather resistance, chemical resistance, transparency, etc., and to provide a multilayer metal! An object of the present invention is to provide an adhesive having strong adhesive strength when adhering materials such as No. 34 resin, ceramics, and wood.

Among them, especially when acrylic monomer penetrates into the adhered object, the secondary adhesive object may be fluororubber or acrylic! 3 {Resistance to styrene? 3. In the case of adhesives, the purpose is to provide adhesives that exhibit even better contact properties.

(Means for Solving the 5 Problems) The present invention is a high polymer obtained by dissolving a fluoropolymer that is soluble in an acrylic monomer in 7 acrylic monomer, and then subjecting it to polymerization or further converting it into IPN. The present invention relates to an adhesive characterized by containing a molecular substance. Homogeneous integration of the fluorine-containing polymer and the 7-acrylic polymer 1 solves the above problem.

In the present invention, the fluorine-containing polymer that can be used is one that is soluble in the acrylic monomer, such as Kitashige's fluorine-containing polymer, which is made of vinyl fluoride.

The vinylidene fluoride copolymer preferably has a number average molecular weight of 5 to 1 million, and contains vinylidene fluoride and other moles that can be copolymerized with it. Or a copolymer of two or more monomers, typical examples of other monomers include tetra-7-fluoroethylene, chloro-trifluoroethylene, tri-7-fluoroethylene, vinyl-7
Luolite, hexa-7-fluoropropylene, penta-7-fluoropropylene, hexa-7-fluoroinbutene, per-7-fluorocycloptene, per-7-fluoro (methylcyclopropylene), per-7-fluoro-7-lene, α,β,β-triple orostyrene, Per-7-fluoro styrene, poly-7-fluoroalkyl vinyl ethers (e.g., per-7-fluoro (methyl vinyl ether), per-7-fluoro (propylene vinyl ether), etc.), poly-7-fluoroacrylic acid or its ester, poly-7-fluoro vinyl acetic acid or its ester, Examples include 7-fluorobinylethenolesulfonic acid, poly-7-fluoro-tf-noenes, ethylene, propylene, acrylic acid or its ester, vinyl acetic acid or its ester, and the content thereof is not particularly limited, but is usually 10 to 60 wt.
% is preferred. Also, among these, the polymers frequently contain iodine Tt. Those that combine atoms or bromine atoms (for example, JP-A-5
3-125491, Japanese Patent Publication No. 53-41153, and Japanese Patent Application Laid-open No. 59-20310) are preferable in terms of increasing polymerization reactivity. Furthermore, the vinylidene fluoride copolymer brought into contact with the acrylmo 77- may be crosslinked by a conventional method.

In addition, other fluorine-containing copolymers include copolymers of tetra-7-fluoroethylene and propylene, ternary copolymers of these and vinylidene fluoride, copolymers of hexa-7-fluoropropylene and ethylene, Examples include a copolymer of fluorovinyl ether and ole7yne, and a 7fluorophos7azene polymer.

In the present invention, the type of 7-acrylic monomer is not limited as long as it dissolves the fluorine-containing polymer, but mono- or polyfunctional monomers are included, and preferably, for example, acrylic acid, methacrylic acid, methyl/tacryl}( MM
A), ethyl methacrylate (EMA), butyl methacrylate (B MA ), 2-hydroxyethyl methacrylate (HEMA), 3-(trinotoxysilyl)
proyl methacryly} (MSPM), 2-(7enylphosphoryl)ethyl methacryly} (pl+enyl
-P), 2-hydroxy-3-(β-na7toxy)probyl methacrylate (FfNPM), N-7enyl-N-(2-hydroxy-3-methacryloxy)probylglycine (NPC-GMA), ethylene glycol no methacrylate (EDMA or IG),
diethylene glycol dimethacrylate} (DiEDMA)
), triethylene glycol dimethacrylate} (Tri
EDMA), 1,4-butanediolnomethacrylate'
r (1.4-BuDMA), 1,3-butanediol dimethacryly} (1.3-BuDMA)
, 2,2-bis(4-(2-hydroxy-3-methacryloxypropoxy)7enyl)propane (Bis G
MA), 2,2-bis(4-methacryloxy7enyl)
Propane (BPDMA), 2,2-bis(4-methacryloxyethoxy7enyl)furopane (Ris ME
PP), 2.2-bis(4-methacryloki?bolyethoxy7enyl)furopane (Bis-MPEPP), 2-(methacryloxethyl)trimethylhexatylene diurethane (UDMA), }limethylolpropane trinotacrylate} (TMPT) ), CIl■=C(CI+,)CO
OCH! C.F. (3FMA), CI12 = C(
Cfls ) COOCl12CF2CF211 <
4 F M A ), CIl■= C(CI1, )C
OOCI12CF2CFyu (5FMA), C+12=
C(CI1,)COOCII■(CF2)2CF,
(7 I'M A), CI12=C(CI1,)
COOCI+2 (CF2), CF,,I+ (8FM
A), each of these corresponding 7 acrylates and each α-7 fluoro acrylate can be exemplified, and one type or a mixture of two or more types of these can be used. Particularly preferred are MMA and 2'' fluorine acrylic monomer.

In the present invention, bonding can be achieved by dissolving the above-mentioned hepta-containing polymer in an acrylic monomer, and then subjecting it to polymerization or further converting it into rPN, in the presence of a polymerization initiation source, Furthermore, polymerization inhibitors, reducing agents,
Transfer agents and the like can also be added. In addition to light and heat, polymerization initiation sources include penzoyl peroxide, azoisobutyronitrile (AIBN), and can-7-arquinone (CQ).
), 9-7 fluorine/ton, tributylborane (TBB), etc., and reducing agents such as nomethylamino/ethyl methacrylate (DMAEMA), dimethyl-p-toluinone (r)MPT), etc. Examples of the polymerization inhibitor include hydroquinone and hydroquinone methyl ester, and examples of the transfer agent include lauryl mercabutane.

rPN (Inter-penetrating Poly
merN etwork) is a polymer formed by mixing the chain polymers of Honmai 2l1 in a liquid state (a solution may be used), crosslinking both or one of them, and intertwining the molecular chains with each other.

In order to proceed with IPN formation, it is necessary to carry out crosslinking, and for example, the above-mentioned vinylidene fluoride copolymer is used which has been crosslinked in advance by a conventional method (at this time, the polymer chain is (It is preferable to use a monomer with bonded atoms.), use of a bifunctional or more functional acrylic monomer, or use of a cross-linked V4 agent. For the first two, the ones already listed can be used. As the crosslinking agent, polyfunctional unsaturated compounds such as tri7lyl isocyanurate, trilyl7lyl cyanurate, triacryl formal, triallyl trimellitate, and noaryl phthalate can be used. Further, at this time, the adhesive strength, solvent resistance, etc. can be further improved by converting the IPN to an organic peroxide as a radical source.

Since the adhesive cutting method of the present invention uses a Mo77 solution of a heptadium-containing polymer, the adhesive penetrates into the target object, and as a result, strong adhesive strength can be obtained. Although the adhesive of the present invention can be used as a single solution, it is preferable to prepare two separate solutions by adding an initiator and a reducing agent to the fluorine-containing polymer and acrylic heptamer solutions, respectively, and mix both solutions immediately before use. It is better to use a method of mixing.

In the present invention, when the polymerization reaction is carried out by heating, for example, by heating at a temperature of about 55 to 100°C for about 10 to 150 minutes; It is preferable to polymerize for several minutes to several tens of minutes.

The loss average molecular weight of the polymer material of the present invention obtained by the above polymerization is preferably in the range of about 1,000 to 300,000.

Although the reason for this is unknown, the polymeric material obtained by the present invention has extremely little residual acrylic monomer, and especially in the range where the ratio of the monomer to the monomer of the hepta-containing polymer exceeds the same amount, the residual monomer is In contrast, when polymethyl methacrylate was dissolved in methyl methacrylate and polymerized, the residual molymer/mer was 0.5% in heat polymerization and 2.4% in monopolymerization. Ta. As described above, residual mo7mer is not detected in the adhesive containing the polymeric substance of the present invention, or the amount thereof is extremely small, so that it is useful as an adhesive for biological materials, etc. In addition, it is also possible to use the polymeric substance obtained in the present invention by treating it with a solvent and making it into a liquid or paste form.

The adhesive of the present invention may also contain fillers, catalysts, dilution agents, coupling agents, etc., as required.

Examples and comparative examples will be described below. Note that % indicates weight %. Example I Liquid A G80]. /MMA/BPO=1/I/O. 02
(Heavy {part i) B liquid G801. /MMA/DMPT=1/1/0.0
2 (heavy fi part) Here, G801 is Guyel@G801 (iodine-containing vinylidene fluoride-based elastic copolymer), MMA is methyl methacrylate}. BPO is penzoyl peroxide, and DMPT is nomethyl-11}luidine.

After punching out cross-sulfurized G801 into a No. 4 dumbbell piece and cutting the center part with a cutter, Al and B liquids are mixed at a ratio of 1:1 (weight ratio), and immediately applied to the adhesive surface and bonded.

After leaving it at room temperature for 1 hour, 500fiI1l with autograph
The tensile strength at break was determined under the conditions of /min: 82kg
/c1.

Comparative Example 1 When adhesive was used, the tensile strength at break was 55 kg/c
It was "m".

Example 2 20X 2X 70111111 plate-shaped cross-sulfurized G80
1 was cut at the middle hole part, and the assembled parts A and B were added in the same manner as in Example 1.
They were adhered in the same way using liquid. Place the sample in boiling water for 13 minutes.
Strong adhesion was observed even after being left for 8 hours.

Comparative Example 2 When an epoxy adhesive was tested under the same conditions as Example 2, the adhesive strength decreased to the point that it could be broken with bare hands after 6 hours.Example 3 A 10 x 2 x 40 mm plate-shaped acrylic plate was tested. 2 pieces,
Bonding was carried out in the same manner as in Example 1 using the same 8 parts and B part so that the adhesion cross-sectional area was 1 cm2. After being left at room temperature for 1 hour, it was pulled at 500 mm/min using an autograph, and the acrylic plate broke, indicating strong adhesion.

Example 4 Liquid A G801/MMA/IG/TA IC/2.5B
/B P O = 1 /0.95/0.05/0.0
4/0.015/0.02 (parts by weight) B liquid Cz801/MM A/ I G/T A I
C/2.5B/D M P T = 1 /0,95/
0.05/0.04/0.015/0.02 (parts by weight) where 1G is ethylene glycol dimethacrylate, T
AIC is triallyl isocyanurate, and 2.5B is Perhexa 2.5B (manufactured by NOF Corporation, peroxide).

After punching cross-sulfurized G801 into a No. 4 dumbbell piece and cutting the center part, Ae. ．． 13fi to l:1 (weight ratio)
Mix with , then immediately apply to the adhesive surface and adhere.

After being left at room temperature for 1 hour, it was heated at 160° C. for 10 minutes to polymerize. The tensile strength at break was determined using Saiichi Togura 7 at 500 #lm/min for 1 cow and found to be 96 kg/cIn2.

Comparative Example 3 When adhesive was bonded using an epoxy # adhesive under the same conditions as in Example 4, the tensile strength at break was 55 kg/em'.

(that's all) Sender: Daikin Industries, Ltd.

Claims (2)

[Claims] (1) An adhesive characterized by containing a polymeric substance obtained by dissolving a fluorine-containing polymer soluble in an acrylic monomer and then subjecting it to polymerization or further converting it into IPN. . (2) The adhesive according to claim 1, wherein the fluorine-containing polymer is a vinylidene fluoride copolymer.