CN103951789B

CN103951789B - A kind of resistant to elevated temperatures minute surface silver resin and preparation method thereof

Info

Publication number: CN103951789B
Application number: CN201410137281.5A
Authority: CN
Inventors: 段泽智
Original assignee: 广州伊德尔化学科技有限公司
Priority date: 2014-04-04
Filing date: 2014-04-04
Publication date: 2017-03-15
Also published as: CN103951789A

Abstract

The invention discloses a kind of resistant to elevated temperatures minute surface silver resin, which is made up of following raw material：First component：Acetylbutyrylcellulose, solvent；Second component：Methyl methacrylate, methacrylic acid butyl acetate, hydroxyethyl methacrylate, hydroxy propyl methacrylate,（Methyl）Acrylic acid epoxy ester, vinylsiloxane, isobornyl methacrylate, lauryl methacrylate, acrylic acid, initiator；Third component：Initiator, solvent.The preparation method of the minute surface silver resin, including step：Acetylbutyrylcellulose in first component is added in solvent and is dissolved, heated while stirring, be warming up to 70 95 DEG C, lead to nitrogen；Second component is mixed, the first component is added drop-wise to, is incubated, is warming up to 85 110 DEG C；Add third component, insulation, finally cooling, filtration.Minute surface silver resin prepared by the present invention has resistance to elevated temperatures, and there is the adhesive force of wide spectrum to base material, and the solvent resistance of product is preferable, and synthesis technique environmental protection.

Description

A kind of resistant to elevated temperatures minute surface silver resin and preparation method thereof

Technical field

The present invention relates to a kind of resistant to elevated temperatures minute surface silver resin and preparation method thereof.

Background technology

Minute surface silver resin is generally acrylic resin modified, minute surface silver resin of the prior art often exist following these One or more in problem：1. resistance to elevated temperatures is not fully up to expectations, the substrate adhesion 2. without wide spectrum, i.e., resin is the bottom of to The adaptability of material is often bad, and 3. the solvent resistance of resin is poor, and 4. raw materials used or synthesis technique is not environmentally；5. synthesize work Skill is relatively costly.

For this purpose, forefathers have done substantial amounts of research work, Chinese patent CN102432777A first synthesizes active acetic acid Cellulose butyrate intermediate, then again with functional acrylic monomer copolymerization, step is more, high cost.

Chinese patent CN101157813A, be acetylbutyrylcellulose acrylic resin etc. be directly mixed to prepare, belong to altogether Mixed modification, during without chemical reaction.

《Acrylic acid modified acetylbutyrylcellulose is used for imitative plating aluminium paint》In one text, changed using Solution Free Radical method Property, monomer used is styrene, methyl methacrylate, ethyl acrylate, methacrylic acid butyl acetate.If according to this article The polymer that the method that offers is made is not then curable.

Content of the invention

It is an object of the invention to provide a kind of resistant to elevated temperatures minute surface silver resin and preparation method thereof.

The technical solution used in the present invention is：

A kind of resistant to elevated temperatures minute surface silver resin, which is made up of the raw material of three below component：First component：Acetate butyrate Cellulose 50-60 parts, solvent 200-300 parts；Second component：Methyl methacrylate 40-50 parts, methacrylic acid butyl acetate 20-30 parts, hydroxyethyl methacrylate 20-25 parts, hydroxy propyl methacrylate 10-15 parts,（Methyl）Acrylic acid epoxy Ester 30-40 parts, vinylsiloxane 0-15 parts, isobornyl methacrylate 0-15 parts, lauryl methacrylate 0-20 parts, Acrylic acid 0-2 parts, initiator 1-2 parts；Third component：Initiator 1-2 parts, solvent 20-30 parts.

Described acetylbutyrylcellulose be CAB381-0.1, CAB381-0.5, CAB381-2, CAB381-20 in extremely Few one kind.

Described initiator is oil soluble peroxides or azo-compound.

Described oil soluble peroxides be benzoyl peroxide, peroxidized t-butyl perbenzoate, cumyl peroxide, At least one in di-t-butyl peroxide, methyl ethyl ketone peroxide.

Described azo-compound is azodiisobutyronitrile, at least one in 2,2'-Azobis(2,4-dimethylvaleronitrile).

Described solvent is esters solvent, ketones solvent, at least one in aromatic hydrocarbon solvent.

Described solvent be ethyl acetate, butyl acetate, glycol methyl ether acetate, ethylene glycol ether acetate, the third two In alcohol methyl ether acetate, butyl acetate, hexone, Ketohexamethylene, butanone, toluene, dimethylbenzene extremely Few one kind.

A kind of preparation method of resistant to elevated temperatures minute surface silver resin, including step：By the acetate butyrate fiber in the first component Element is added in solvent and dissolves, and heats while stirring, is warming up to 70-95 DEG C, leads to nitrogen protection；Will be complete for the material in the second component Portion mixes, and is added drop-wise in the first component with 3.5-4.5 hours, is incubated 1-1.5 hours, is warming up to 85-110 DEG C；Add the 3rd group Point, 2-2.5 hours are incubated, finally cooling, filtration.

The invention has the beneficial effects as follows：Minute surface silver resin prepared by the present invention has resistance to elevated temperatures, base material is had wide The adhesive force of spectrum, the solvent resistance of product are preferable, and synthesis technique environmental protection.

Description of the drawings

Fig. 1 be the embodiment of the present invention 3 synthesis minute surface silver resin mirror effect test in, spray on glass dry after Picture in kind.

Specific embodiment

A kind of resistant to elevated temperatures minute surface silver resin, which is made up of the raw material of three below component（Described part is quality Part）：First component：Acetylbutyrylcellulose 50-60 parts, solvent 200-300 parts；Second component：Methyl methacrylate 40-50 Part, methacrylic acid butyl acetate 20-30 parts, hydroxyethyl methacrylate 20-25 parts, hydroxy propyl methacrylate 10- 15 parts,（Methyl）Acrylic acid epoxy ester 30-40 parts, vinylsiloxane 0-15 parts, isobornyl methacrylate 0-15 parts, first Base lauryl acrylate 0-20 parts, acrylic acid 0-2 parts, initiator 1-2 parts；Third component：Initiator 1-2 parts, solvent 20-30 Part.

The preparation method of above-mentioned resistant to elevated temperatures minute surface silver resin, including step：Will be fine for the acetate butyrate in the first component Dimension element is added in solvent and dissolves, and heats while stirring, is warming up to 70-95 DEG C, leads to nitrogen protection；By the material in the second component All mix, be added drop-wise in the first component with 3.5-4.5 hours, be incubated 1-1.5 hours, be warming up to 85-110 DEG C；Add the 3rd Component, is incubated 2-2.5 hours, finally cooling, filtration.

Preferably, described acetylbutyrylcellulose is CAB381-0.1, CAB381-0.5, CAB381-2, CAB381-20 In at least one.

Described initiator is oil soluble peroxides or azo-compound；Preferably, described oil soluble peroxides For benzoyl peroxide, peroxidized t-butyl perbenzoate, cumyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide In at least one；Described azo-compound is azodiisobutyronitrile, at least one in 2,2'-Azobis(2,4-dimethylvaleronitrile).

Described solvent is esters solvent, ketones solvent, at least one in aromatic hydrocarbon solvent；Preferably, described molten Agent is ethyl acetate, butyl acetate, glycol methyl ether acetate, ethylene glycol ether acetate, propylene glycol methyl ether acetate, diethyl At least one in glycol monobutyl ether acetate, hexone, Ketohexamethylene, butanone, toluene, dimethylbenzene.

With reference to specific embodiment, the present invention is described further：

Embodiment 1:

Lead to nitrogen in four-hole boiling flask, add 200 parts of butyl acetates, 50 parts of dimethylbenzene to heat while stirring, be subsequently adding 50 parts of CAB381-2 dissolvings, are warming up to 80 DEG C.Start the following mixture of Deca, 40 parts of methyl methacrylates 20 parts of methyl-props Olefin(e) acid butyl acetate 10 parts of hydroxyethyl methacrylates 10 parts of hydroxy propyl methacrylates 40 parts of glycidyls Ester 1 part of initiator azodiisobutyronitrile, dripped off with 4 hours, after dripping off be incubated 1 hour.Again by 1 part of azodiisobutyronitrile 20 parts Butyl acetate is added, and is incubated 2 hours, is filtered.

Embodiment 2:

Lead to nitrogen in four-hole boiling flask, add 300 parts of glycol methyl ether acetates, heat while stirring, be subsequently adding 50 Part CAB381-20 dissolvings, are warming up to 85-90 DEG C.Start the following mixture of Deca, 50 parts of methyl methacrylates 20 parts of methyl Acrylic acid butyl acetate 10 parts of hydroxyethyl methacrylates 10 parts of hydroxy propyl methacrylates 30 parts of methacrylic acid rings Oxygen ester 10 parts of isobornyl methacrylates 1.5 parts of benzoyl peroxides mixing, dripped off with 4 hours, after dripping off, insulation 1 is little When.Again by 1 part of benzoyl peroxide 20 parts of butyl acetates add, be incubated 2 hours, filter.

Embodiment 3:

Lead to nitrogen in four-hole boiling flask, add 200 parts of glycol methyl ether acetates, 100 parts of dimethylbenzene to stir in heating Mix, be subsequently adding 60 parts of CAB381-0.5 dissolvings, be warming up to 85-90 DEG C.Start the following mixture of Deca, 45 parts of methacrylic acids Methyl ester 20 parts of methacrylic acid butyl acetates 10 parts of hydroxyethyl methacrylates 15 parts of hydroxy propyl methacrylates 40 Part epoxymethacrylate, 10 parts of VTESs 1 part of azodiisobutyronitrile 0.5 part of benzoyl peroxide, Dripped off with 4 hours, after dripping off, be incubated 1 hour.Again by 1 part of benzoyl peroxide 20 parts of butyl acetates add, be incubated 2 hours, mistake Filter.

Following test is carried out to the resin of present invention synthesis：

First, resin adhesive force test

Electrosilvering proportioning：15 mass parts of resin of the synthesis of embodiment 3,3 mass parts of minute surface silver paste, solvent ethylene glycol methyl ether vinegar 82 mass parts of acid esters；Mirror-like silver proportioning：1 mass parts of resin of the synthesis of embodiment 3,2 mass parts of minute surface silver paste, solvent ethylene glycol first 17 mass parts of ether acetate.

Form of construction work：Spraying；Drying mode：70 DEG C are toasted 1 hour.

Following test result is obtained in electroplating effect test and mirror effect test

Ground	Glass	PC	PET	ABS	PS
						Adhesive force grade	0 grade	0 grade	1 grade	0 grade	1 grade

Fig. 1 be the embodiment of the present invention 3 synthesis minute surface silver resin in this secondary mirror measure of merit, spray on glass do Picture in kind after dry.

2nd, resin high temperature test

Test mode：The resin sample of embodiment 1-3 synthesis directly toasts 30 parts at 180 DEG C, and visualization of color changes.

Test result：It was found that obvious color change

3rd, resin recoating examination

Construction proportioning

Ink with mirror effect：Embodiment 2-in-1 into 1 mass parts of minute surface resin, 2 mass parts of silver paste, 17 mass parts of Tianna solution；

PU varnish：PU 5 mass parts of resin, 1.6 mass parts of TDI firming agent, 5 mass parts of Tianna solution；

Baking vanish varnish：Baking vanish 5 mass parts of resin, 5 mass parts of Tianna solution；

Form of construction work：Ink with mirror effect is sprayed on glass first, is toasted 30 minutes in 150 DEG C；Difference is painted again in minute surface Spraying PU varnish or baking vanish varnish, PU varnish-dryings mode be 70 DEG C 30 minutes, baking vanish be 130 DEG C 30 minutes.

Test result：PU varnish, baking vanish varnish adhesive force on ink with mirror effect reaches 0 grade.

4th, solvent resistance test

Solvent resistance（Butanone is wiped）：100 times.

Claims

1. a kind of resistant to elevated temperatures minute surface silver resin, it is characterised in that：Which is made up of the raw material of three below component：First group Point：

Acetylbutyrylcellulose 50-60 mass parts, solvent 200-300 mass parts；Second component：Methyl methacrylate 40-50 Mass parts, methacrylic acid butyl acetate 20-30 mass parts, hydroxyethyl methacrylate 20-25 mass parts, methacrylic acid Hydroxy propyl ester 10-15 mass parts,（Methyl）Acrylic acid epoxy ester 30-40 mass parts, vinylsiloxane 0-15 mass parts, methyl Isobornyl acrylate 0-15 mass parts, lauryl methacrylate 0-20 mass parts, acrylic acid 0-2 mass parts, initiator 1-2 Mass parts；Third component：Initiator 1-2 mass parts, solvent 20-30 mass parts.

2. a kind of resistant to elevated temperatures minute surface silver resin according to claim 1, it is characterised in that：Described acetate butyrate fiber Element is at least one in CAB381-0.1, CAB381-0.5, CAB381-2, CAB381-20.

3. a kind of resistant to elevated temperatures minute surface silver resin according to claim 1, it is characterised in that：Described initiator is oil soluble Property peroxide or azo-compound.

4. a kind of resistant to elevated temperatures minute surface silver resin according to claim 3, it is characterised in that：Described oil-soluble peroxidating Thing is benzoyl peroxide, peroxidized t-butyl perbenzoate, cumyl peroxide, di-t-butyl peroxide, peroxidating first and second At least one in ketone.

5. a kind of resistant to elevated temperatures minute surface silver resin according to claim 3, it is characterised in that：Described azo-compound is At least one in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).

6. a kind of resistant to elevated temperatures minute surface silver resin according to claim 1, it is characterised in that：Described solvent is that esters are molten Agent, ketones solvent, at least one in aromatic hydrocarbon solvent.

7. a kind of resistant to elevated temperatures minute surface silver resin according to claim 6, it is characterised in that：Described solvent is acetic acid second Ester, butyl acetate, glycol methyl ether acetate, ethylene glycol ether acetate, propylene glycol methyl ether acetate, butyl vinegar At least one in acid esters, hexone, Ketohexamethylene, butanone, toluene, dimethylbenzene.

8. the preparation method of a kind of resistant to elevated temperatures minute surface silver resin described in claim 1, it is characterised in that：Including step：Will Acetylbutyrylcellulose in first component is added in solvent and dissolves, and heats while stirring, is warming up to 70-95 DEG C, leads to nitrogen Protection；Material in second component is all mixed, is added drop-wise in the first component with 3.5-4.5 hours, be incubated 1-1.5 hours, It is warming up to 85-110 DEG C；Third component is added, 2-2.5 hours are incubated, finally cooling, filtration.