JPS58196279A - Storage-stable miscible hardening agent for acrylic acid resin adhesive and manufacture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a process for making storage stable hardeners for acrylic adhesives that are miscible with acrylic resins.

It relates to the hardener obtained by the method and to the use of this hardener in mixtures with acrylic resin adhesives.

Reactive acrylic acid adhesives are two-component adhesive systems that can be polymerized at room temperature and consist of 1) a resin containing a free radical-forming compound, and ii) a curing agent. In this case, the resin and the curing agent are in principle applied separately to the parts to be bonded; the applied parts are then bonded and the adhesive layer is then cured.

On the one hand, this simple method has many technical advantages, but on the other hand, it can lead to difficult-to-adjust variations in the strength of its adhesion. This variation in strength is caused by the hardening agent after the resin and hardener are combined.

This is due to the curing process, which is dependent on diffusion into the resin layer.

It has also been shown that reactive acrylic resin adhesives can be cured when mixed together with a curing agent (an amine/aldehyde adduct formed from aluminum and butyraldehyde), which are generally used separately. Confirmed. The quantitative ratio of resin to hardener required for sufficient adhesion is approximately 100:5. However, this ratio.

If mechanical feeding is done in fixed quantities.

In addition, the viscosity values of the resin and the hardener are very different (resin 8-40 Pa-s, hardener 200 mPa-5), which makes it difficult to control the viscosity of the resin and the hardener. It is difficult to homogeneously mix dilute liquid hardeners when applying the adhesive components manually, which requires dividing very large amounts into different amounts, making this method too complicated. @Also, when the components are applied separately, it is even more troublesome because one reaction partner is not enough, so they do not adhere to each other and remain uncured. All portions of resin and hardener must be removed from the adhesive product.

In the specification of United States Patent No. 4,540,552,
An acrylic resin adhesive and hardener are described that are mixed together in a 1:1 ratio. These mixtures were developed for use in the dental field, and for industrial applications they suffer from the disadvantage that one component is liquid and the other powder, making them difficult to mix. have

In fact, curing agents containing vinyl monomers, amine/aldehyde condensates, stabilizers, and polymers are commercially available, but their viscosity increases in a relatively short period of time, so their storage stability is Often unsuitable for application.

The curing agents produced according to the invention are viscosity-stable and even reactive. That is, it has been found that the polymers are still capable of polymerization.

In the method of the present invention, a thermoplastic resin or an elastomer soluble in each skeleton monomer is added to a polymerizable monomer containing an olefinic group at a temperature of 50 to 100°C, optionally with a stabilizer; It consists of adding a liquid aldehyde/amine condensate to a viscous solution; and homogenizing the solution at elevated temperatures. Preferably, the thickened solution is cooled before adding the aldehyde/amine condensate. The homogenization is preferably carried out at a temperature of 6°C to 100°C ◇ As polymerizable monomers, the following are preferred, for example: nia acrylate, methacrylate, styrene, chlorostyrene, 2-chloro-1,3-butadiene and 2-chloro-1,3-butadiene. .5-dichloro-1,5-7'tadiene: especially methyl-, ethyl- or butyl methacrylate and methacrylo-2
-Ethoxyethyl ester is preferred.

Liquid aldehyde/amine condensate Fi that can be used
: With formaldehyde, acetaldehyde, propionaldehyde, hexaaldehyde, heptaldehyde or crotonaldehyde.

Primary or secondary, aliphatic or aromatic
Item 1: For example, ethylamine, n-butylamine.

n- and iso-propylamine, n-hexylamine,
t-Butylamine, p-toluidine.

It is formed from xylidine or benzylamine, as well as diethylamine and diphenylamine. Preferably, a reaction product consisting of aniline and butyraldehyde is used, with a concentration of 1 to 45% per mole of aniline.
Moles, preferably 15 to 3.0 moles of butyraldehyde are used.

As stabilizers, preference is given to using quinoline-like compounds, especially quinoline itself, in amounts of α005 to 15% by weight, based on the hardener. The need to use stabilizers depends on the reactivity of the monomeric compounds.

For example, when using butyl acrylate, a stabilizer is not required (and can of course be present); whereas when using, for example, methyl methacrylate, a stabilizer is required. The preferred thermoplastic resin for use is polyacetal. ,
Polyacrylates, polymethacrylates, polystyrenes or polyamides, or copolymers of styrene and acrylates or methacrylates, copolymers of styrene and butadiene or copolymers of styrene and isoprene, or styrene.

Terpolymers from butadiene and acrylonitrile used in amounts of 5 to 85% by weight, preferably 5 to 55% by weight, based on the curing agent.

Preferred elastomers include: polyurethane, butyl rubber or butadiene/acrylonitrile copolymers, and from 5 to 85% by weight based on the curing agent.
, preferably in an amount of 5 to 55% by weight.

The amount of thermoplastic resin or elast 1- in the curing agent is
It depends on the desired viscosity of the curing agent.

The value of this viscosity is advantageously matched to the viscosity of the acrylic resin adhesive, ie approximately 4 to 30 Pa-a.

The method of the present invention also applies. It is also possible to add transition metal compounds as promoters during adhesion.

Such compounds include metal-containing compounds 2 in the form of chelate compounds, such as β-diketones or ethylene- or propylene diamines.

or metal-containing compounds in the form of compounds of organic acids or alcohols, such as naphthinates (e.g. cobalt, nickel i9 as manganese-containing compounds), octoates (e.g. as steel-containing compounds), hexoates and propionates (e.g. as iron-containing compounds). ), are included. Preferred materials are acetylacetonates of vanadium, steel, cobalt and iron.

For example: Cu(II)-acetylacetonate, C
Also mentioned are u-p-) luenesulfinate and Cu-naphthinate. They have α000 relative to the curing agent
It is added in an amount of 5 to 10 parts by weight.

Surprisingly, the curing agent mixture remains stable with respect to viscosity and activity even when accelerators of the type mentioned above are added, and when quinone is present as a stabilizer. The same applies to

Acrylic acid resin adhesives can also be produced, for example, according to US Pat. No. 4,278,106 ◎ Production of acrylic acid resin adhesive A: 58 parts by weight of methyl methacrylate, 10 parts by weight of methacrylic acid, 1 part by weight of ethylene glycol dimethacrylate ,
5 parts by weight of quinone α and 27 parts by weight of acrylonitrile/butadiene/styrene copolymer powder are dissolved at 50° C. under nitrogen. Then chlorsulfophenylmaleimide 2
Add part by weight at room temperature and stir the mixture for 1 hour. Then add 1 part of cumene hydro/so oxide and 1 part of butylene glycol diglyside CLS and homogenize the mixture. Brookfield viscosity of A (using spindle A4,
50 r, p, m) is 8 to 12 Pa・8
It is.

The curing agent contains 10 to 90% by weight, preferably 60 to 80% by weight of polymerizable monomer, 5 to 25% by weight, preferably 10 to 18% by weight, of aldehyde/amine condensation based on the total amount of the curing agent. material, 5 to 85 weight-1
Preferably from 1110 to 20% by weight of thermoplastic resin or elastomer, and optionally stabilizers and/or metal compounds in predetermined amounts.

"Part" in the following examples represents 1 part by weight.Example 1
: Production of a slow-release curing agent that can be mixed with a resin adhesive at a ratio of 1=1 64.7 parts of methyl methacrylate and 3 parts of quinone α,
Mix thoroughly at room temperature under nitrogen in a female 7 flask with a stopper. Then, 20 parts of polyacetal is added, and the liquid mixture is stirred at -80°C for 1 hour.
; Measured with an Oswald viscosity needle. 1 in 95% ethanol
The viscosity of the solution was 55 mPa-5). The solution was then cooled to room temperature and the condensation product formed from aniline and butyraldehyde ([Panax
x) Add 15 parts of a product consisting of approximately 40 parts of 808J■). The solution is homogenized at 80° C. for 2 hours and cooled. This curing agent can be mixed with the resin adhesive A at any mixing ratio within the range of 2:1 to 1:2 (accurate metering is not required) depending on the desired curing time. The Brookfield viscosity of this curing agent is 8 Pa-
g and 10 Pa-s after storage for 7 days at 60°C.

Example 2: Preparation of a fast-acting curing agent that is miscible with the resin in a 1:1 ratio, except that 0.05 parts of copper acetylacetonate Q is added to the amine/aldehyde condensation product and the solution is heated. The general method of Example 1 is carried out.

Before storage at Brookfield Viscosity Co., Ltd., the pressure was 6Pa.3. And after storage at 60°C for 7 days, it is 7 Pa-s.

Example 5: The method described in Example 2 is carried out, except that 005 parts of copper p-)luenesulfate α005 is mixed instead of copper acetylacetonate.

This Brookfield viscosity is F19Pa-s before storage,
Example 4: Instead of 20 parts of polyacetal, the same amount of polyurethane elastomer (the Brookfield viscosity of this polyurethane in a solution of 15% in ethyl methyl ketone at 23°C is 16
Example 1 except that 2PIL-s)
This will be carried out using the method described in the previous section.

The Brookfield viscosity was 26 Pa-s before storage.
and Fi22Pa-s after storage at 60°C for 7 days.

Example 5: Amine/aldehyde condensate (copper acetylacetonate)
The same procedure as described in Example 4 is carried out except that 005 parts of Q.

This Brookfield viscosity is 28 Pa-s before storage.
, and 20 pa-s after storage for 7 days at 60°C.

The properties of a 1:1 mixture of acrylic resin adhesive A and the curing agent of Examples 1 to 5 are shown in Table 1 below.For its curing, fresh acrylic resin A' is used in each case. . The substrate used is a degreased aluminum sheet.

To determine the initial adhesion, its curing agent.

This initial adhesion is used in the freshly prepared state.

The zero tensile shear strength was determined by the time from the time the coated sheets were placed together until the time the sheets just adhered to each other without separating. Therefore, for the mixture with acrylic acid resin, the value using the freshly prepared hardener is K in the first box ("0 value"), and the same hardener is 60
The second frame is the value stored at ℃ for 7 days (7 days/60℃)
This measurement is carried out 45 or 60 minutes and 24 hours after mixing at room temperature (rRTJ').

Table I After 60 minutes (RT) Example 6 to 9: 64.7 parts of methyl methacrylate and quinone αS part,
Thoroughly mix at room temperature under nitrogen in a volumetric flask with a stopper; and then add 20 parts of polymerizable monomer as a thickener. After dissolving these components, add 15 parts of amine/aldehyde adduct and optionally metal salt and homogenize the mixture at 80°C for 2 hours. The quinone+amine/aldehyde condensation product is insoluble in methyl methacrylate. It is very important to observe carefully after adding the starting materials as a precipitate will form. The initial value of the viscosity of the prepared curing agent and the value after storage at 60° C. for 7 days are shown.

Table 3 shows the tensile strength of the adhesive phase with acrylic resin A after curing at room temperature for 45 minutes and 24 hours for Examples 6 to 59.

Using the newly prepared curing agent, place the good value in the first frame (HA),
The values obtained when the same curing agent was stored at 60° C. for 7 days are shown in the second frame (HB). In these tests, degreased aluminum sheets were glued.

Table ■ Table fl (continued) Table ■ (continued) Detachment = delamination, that is, things that did not adhere. Also from Table ■. It can also be seen that metal salts have an adhesion promoting effect. Patent applicant Chiver Geigy Akchengesellschaft

Claims (1)

[Scope of Claims] (1) Five olefinic groups optionally containing a stabilizer are added to a polymerizable monomer at a temperature of 50 to 100°C to form a thermoplastic resin soluble in each monomer. The process consists of adding a resin or elastomer; adding a liquid aldehyde/amine condensate to the thickened solution thus formed; and homogenizing the solution at elevated temperatures. A method for producing a storage stable curing agent for reactive acrylic adhesives that is miscible with acrylic resin adhesives. (2) Before adding the aldehyde/amine condensate. 2. A method as claimed in claim 1, in which the thickened solution is cooled. (3) The method according to claim 1, wherein the homogenization is carried out at a temperature of 60 to 100°C. (4) Add α00 to the mixture based on the total amount of curing agent.
2. A process according to claim 1, wherein an amount of transition metal complex compound of 0.05 to 10% by weight is added as a curing accelerator. (5) The polymerizable monomer used is acrylate, methacrylate, styrene, or chlorostyrene. 2. The method according to claim 1, wherein 2-chloro-1,3-butadiene or 2<3-dichloro-1,3-butadiene is used. (6) The method according to claim 5, using methyl, ethyl-butyl methacrylate or methacrylic acid-2-ethoxy-ethyl ester. (7) The thermoplastic resin used is polyacetal. A copolymer formed from polyacrylate, polymethacrylate, polystyrene or polyamide, or styrene and acrylate or methacrylate, styrene and butadiene or styrene and isoprene, used in an amount of 5 to 95 tik- based on the amount of curing agent. A method according to claim 1. (8) The elastomer used is polyurethane, butyl rubber or butadiene/acrylonitrile copolymer,
2. A method according to claim 1, wherein it is used in an amount of 5 to 85 parts by weight, based on the amount of curing agent. (9) The method according to claim 1, wherein the liquid aldehyde/amine condensate used is one produced from aniline and butyraldehyde. ■ The method according to claim 1, in which quinone as a stabilizer is added to a polymerizable monomer (b) A polymerizable monomer having an olefinic group, which optionally contains a stabilizer,
At a temperature of 50 to 100° C., add a thermoplastic resin or a nidistomer, each soluble in said monomer; add a liquid aldehyde/amine condensate to the thickened solution thus formed;
and a curing agent for a reactive acrylic acid liquid adhesive manufactured by homogenizing the solution at high temperature.(2) Based on the total amount, 10 to 90% by weight of a polymerizable monomer, 5 to 25% by weight of aldehyde/amine condensate, 5 to 85% by weight of thermoplastic resin or elastomer, optionally α0005 to 10% by weight.
and optionally Q, (105
12. A curing agent according to claim 11 containing from 15% by weight of stabilizer. 0 To a polymerizable monomer having an olefinic group, optionally containing a stabilizer, at a temperature of 50 to 100°C, a thermoplastic resin or a diistomer, each soluble in the monomer, is added: thus produced. Liquid aldehyde in thickening solution/
of a curing agent prepared by adding an amine condensate; and homogenizing the solution at high temperature. of the reactive acrylic acid adhesive in a mixture containing the reactive acrylic acid resin adhesive, and in which the quantitative ratio of the acrylic acid resin adhesive to the curing agent is from 2:1 to 1:2. □Usage for.