CN107699099A - A kind of fluorescent visual type electronic protection coating composition and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of fluorescent visual type electronic protection coating composition, and it includes the fluorinated acrylate monomer of 40 90 parts by weight, the non-fluoroacrylate monomers of 1 50 parts by weight, fluorescent monomer, the silane coupler of 0.1 5 parts by weight of 0.01 5 parts by weight.The electronic paint composition of the present invention taken into account low-surface-energy, excellent weatherability, heat resistance and the acrylic resin good dissolubility of fluororesin, adhesive force, it is cheap and easy to get the advantages that.To have fluorescence molecule and silane coupler to be introduced into fluorinated polymer, and make coating more lasting stability, and there is fluorescent visual, and be easy to quality control during detection and film, there is good practical value.According to the coating composition of the present invention, it can be used for various materials, be particularly used as the fluorescent visual type water-repellent paint of the electronic components such as printed circuit board (PCB), hard disk drive component, electronic component, display screen and touch screen element.

Description

A fluorescent visible electronic protective coating composition and preparation method thereof

technical field

The invention relates to the technical field of electronic protective coatings, in particular to a fluorescent visible electronic protective coating composition and a preparation method thereof.

Background technique

With the continuous development of electronic technology, the application of electronic products is becoming more and more extensive, and the protection of various electronic equipment and instruments is becoming more and more important. Increasingly compact and complex electronic devices, such as mobile phones, tablets, walkmans, etc., often malfunction when wetted by water. Especially for electronic components, such as printed circuit boards, electronic components, touch screen components, etc. If there is no proper protection, electronic equipment is prone to short circuit, performance degradation and equipment failure, and it is difficult to operate for a long time with high reliability.

In the prior art, acrylic resins, polyurethanes, and epoxy resins are often used to waterproof electronic components, and there are problems such as difficult coating, long processing time, and low efficiency. The reported fluorine-containing acrylate polymer is used as a waterproof coating composition for electronic equipment. Although it can achieve a good hydrophobic effect, it is not suitable for detection because the coating is thin and transparent, and there are problems such as quality control.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of the prior art, and provide a fluorescent visible electronic protective coating composition and a preparation method thereof. The invention is a transparent, low-viscosity, low-surface tension solution formed by copolymerization of fluorine-containing acrylate, hydrocarbon chain acrylate, silane coupling agent and fluorescent monomer. It can be applied to various materials by dipping, spraying, hanging or brushing, especially for electronic components, and it does not need curing and dries quickly. The formed coating film has extremely low surface tension, excellent waterproof performance and long-lasting stability. In addition, the coating can act as a barrier film around lubricated areas such as automotive bearings and valve stems to inhibit lubricant migration, prevent contamination of nearby sensitive components, and protect equipment. The fluorescent monomer is introduced into the fluorinated polymer, so that the coating has fluorescent visibility and stable fluorescent effect, which is convenient for detection and quality control in the coating process.

The technical scheme adopted by the present invention to solve the technical problem is as follows: a fluorescent visible electronic protective coating composition, which includes 40-90 parts by weight of fluorine-containing acrylate monomers, 1-50 parts by weight of non-fluorine-containing acrylate monomers body, 0.01-5 parts by weight of fluorescent monomer, and 0.1-5 parts by weight of silane coupling agent.

Further, the general structural formula of the fluorine-containing acrylate monomer is:

In formula (1), X is a side group of the main chain, selected from hydrogen atom, halogen atom, cyano group, phenyl, substituted phenyl, alkyl or haloalkyl; Y is a linking group, which can be aliphatic, aromatic Aryl group, aliphatic group containing oxygen atom, aromatic group containing oxygen atom, aliphatic group containing oxygen atom, araliphatic group containing oxygen atom, ester group, -(CH ₂ ) _m -S-, - (CH ₂ ) _m -SO ₂ -, -(CH ₂ ) _m -N(OH)-(CH ₂ ) _n - or -(CH ₂ ) _m -N(C _n H _2n+1 )-SO ₂ -, R is a fluorine-containing group, which is a straight-chain or branched-chain fluoroalkyl group; the above-mentioned fluorine-containing acrylate monomers can be used in combination of one kind or two or more.

Considering environmental protection and solubility, etc., the preferred environment-friendly short fluorocarbon side chain fluorine-containing acrylate monomers of fluorine-containing acrylate monomers, such as perfluorohexyl ethyl acrylate, perfluorohexyl ethyl acrylate, acrylic acid (N- Methylperfluorobutanesulfonamido)ethyl ester, (N-methylperfluorohexanesulfonamido)ethyl acrylate. In order to further improve the water resistance, it is preferable that X is a substituent other than a hydrogen atom, such as a methyl group, a chlorine atom, a fluorine atom, and the like. In particular, when X is a methyl group, the corrosive effect on electronic parts is small and the price is relatively cheap. Further, the non-fluorine acrylate can be selected from butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, isooctyl acrylate, methyl Isooctyl acrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, cetyl methacrylate, octadecyl acrylate, stearyl methacrylate, adamantyl acrylate, norbornene Base acrylate, isobornyl acrylate, dicyclopentyl acrylate and cyclohexyl acrylate, etc.; the above-mentioned non-fluorine acrylates can be used in combination of one kind or two or more.

Further, the fluorescent monomer is selected from the group consisting of fluorescent monomers with an aromatic fused ring structure containing a polymerizable carbon-carbon double bond, fluorescent monomers with a conjugated structure containing a polymerizable carbon-carbon double bond, or metals containing a polymerizable carbon-carbon double bond. With fluorescent monomer. Can be derived from polymerizable carbon-carbon double bond stilbene fluorescent monomers, polymerizable carbon carbon double bond pyrene fluorescent monomers, polymerizable carbon carbon double bond indole fluorescent monomers, polymerizable carbon carbon double bond benzoxazoles Fluorescent monomers, polymerizable carbon-carbon double bond quinoline fluorescent monomers, polymerizable carbon-carbon double bond carbazole fluorescent monomers, polymerizable carbon-carbon double bond naphthalimide fluorescent monomers, polymerizable carbon-carbon double bond Bond coumarin fluorescent monomer, polymerizable carbon-carbon double bond pyrazoline fluorescent monomer, polymerizable carbon carbon double bond anthraquinone fluorescent monomer or polymerizable carbon carbon double bond rhodamine fluorescent monomer, etc. Several fluorescent monomers are listed below:

1) Pyrene compounds

2) Benzoxazole compounds

3) Carbazole compounds

4) 1,8-naphthalimide derivatives

5) Coumarin derivatives

6) Anthraquinone derivatives

The fluorescent monomers of the paint are not limited to the above types, and one kind or two or more kinds of fluorescent monomers can be used in combination.

Further, the general formula of the silane coupling agent is R ₁ SiX ₁ X ₂ X ₃ , where R ₁ is mercapto, mercaptoalkyl, vinyl or (meth)acryloyloxy; X ₁ , X ₂ and _X3 are the same or different alkyl, alkoxy, aryloxy or acyl groups, wherein at least one of X1, X2 and X3 is an alkoxy, aryloxy or acyl group.

Another object of the present invention is to provide a kind of fluorescent visible electronic protective coating composition, it comprises the steps:

(1) 40-90 parts by weight of fluorine-containing acrylate monomer, 1-50 parts by weight of non-fluorine-containing acrylate monomer, 0.01-5 parts by weight of fluorescent monomer, 0.1-5 parts by weight of silane coupling agent and 200-300 parts by weight of fluorine-based solvents are uniformly mixed in a container to obtain a first solution;

(2) In a nitrogen atmosphere, heat the first solution to 60°C-80°C, add 0.1-2 parts by weight of an initiator, keep it warm for 2-6 hours, add 0.1-2 parts by weight of an initiator, and continue React for 2-6h to obtain the second solution;

(3) After the second solution is cooled to 0-40°C, the fluoropolymer is precipitated with methanol, dried under reduced pressure, and the prepared coating composition is dissolved with a fluorine-based solvent.

Further, the fluorine-based solvent is selected from perfluoroacetone, perfluorohexanone, trifluoroacetic acid, perfluorobutyric acid, perfluorovaleric acid, hydrofluoroether, perfluoroalkane, hydrofluoroalkane, hydrochlorofluoroalkane, Perchlorofluoroalkane, perfluorotriethylamine, perfluorotripropylamine, perfluorotributylamine, perfluorotripentylamine, hydrofluoroalcohol, hexafluorobenzene, hexafluorotoluene, hexafluorom-xylene or perfluoro-2 - n-butyltetrahydrofuran and the like. The above solvents may be used alone or in combination of two or more.

The initiator used in the preparation process of the coating composition is not particularly limited, and may be azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, azobisisobutylamidine Azo compound initiators such as hydrochloride can be peroxide initiators such as ammonium persulfate, benzoyl peroxide, benzoyl tert-butyl peroxide, methyl ethyl ketone peroxide, etc., and can also be composite initiation systems, such as Composite initiation system of azobisisobutyronitrile and azobisisoheptanonitrile, composite initiation system of dibenzoyl peroxide and tert-butyl peroxybenzoate, etc.

The solid content in the prepared coating composition is 0.1-10wt%.

The coating composition prepared by the invention can be used for various materials such as plastics, metals, glass, ceramics, etc. to form waterproof coatings with fluorescent visibility. Especially for electronic components, such as printed circuit boards, hard drive components, electronic components, display and touch screen components, etc., it can effectively protect electronic components from water, thereby reducing the possibility of failure caused by water.

There are many ways to use the coating composition, such as dipping, spraying, spin coating and brushing. The treatment temperature can be at room temperature, and the treatment time is 1s-12 hours. Atmospheric drying is all that is required, and usually only takes a few minutes or even seconds to complete the drying step.

Advantage and beneficial effect of the present invention are:

1. A kind of electronic waterproof coating composition with extremely low surface energy that the present invention obtains can be used for the hydrophobic treatment of various materials, especially used as printed circuit boards, hard disk drive components, electronic components, display screens and touch screen components Fluorescent visible waterproof coating for electronic components such as to protect them from water.

2. The present invention can also be used as a barrier film surrounding lubricating areas such as automobile bearings and valve stems to inhibit the migration of lubricants, prevent contamination of nearby sensitive parts, and protect equipment.

3. In the present invention, the environment-friendly short fluorocarbon chain acrylate monomer is preferentially used, which will not cause harm to the environment. In addition, non-fluorine acrylate and silane coupling agent are added to make the adhesion between the coating and the material stronger and more durable and stable.

4. The paint in the present invention takes into account the advantages of low surface energy, excellent weather resistance, heat resistance of fluororesin and good solubility, adhesion, low price and easy availability of acrylic resin. Introducing fluorescent molecules and silane coupling agents into fluorinated polymers makes the coating more durable and stable, and has fluorescence visibility, which is convenient for detection and quality control during the coating process, and has good practical value.

Description of drawings

Fig. 1 is the static water contact angle figure of example 5 and comparative example 1.

detailed description

Through the following five multi-component fluorine-containing acrylate examples, the technical solution of the present invention is described in detail, but the components of the present invention are not limited to the following examples.

Example 1:

(1) Mix 5g of perfluorohexaneethyl methacrylate (C6MA), 4g of octadecyl acrylate, 0.001g of 9-methacrylamidocarbazole, 0.01g of KH570 and 20g of perfluoro-2-n-butyltetrahydrofuran Add a three-necked flask and mix evenly to obtain the first solution;

(2) In a nitrogen atmosphere, heat the first solution to 60°C, add 0.2g of azobisisoheptanonitrile, react for 6 hours, add 0.01g of azobisisoheptanonitrile, continue the reaction for 2h, and obtain the second Second solution.

(3) After the second solution is cooled to 40° C., the fluoropolymer is precipitated with methanol, dried under reduced pressure, and the prepared coating composition is dissolved with perfluoro-2-n-butyltetrahydrofuran.

Example 2:

(1) 4g perfluorobutyl ethyl methacrylate (C4MA), 5g octadecyl acrylate, 0.3g 9-methacrylamidocarbazole, 0.05g KH570 and 25g perfluoro-2-n-butyltetrahydrofuran Add a three-necked flask and mix evenly to obtain the first solution;

(2) In a nitrogen atmosphere, heat the first solution to 65°C, add 0.15g of azobisisoheptanonitrile, react for 5 hours, add 0.03g of azobisisoheptanonitrile, and continue the reaction for 3h to obtain the first Second solution.

(3) After the second solution is cooled to 30° C., the fluoropolymer is precipitated with methanol, dried under reduced pressure, and the prepared coating composition is dissolved with perfluoro-2-n-butyltetrahydrofuran.

Example 3:

(1) Add 7g of (N-methylperfluorohexanesulfonamido) ethyl acrylate (C6SA), 2g of cetyl methacrylate, 0.003g of 1-propenyloxy-4-hydroxyanthraquinone-9,10- Add diketone (AHD), 0.1g KH570 and 30g HFE-458 into a three-necked flask, and mix uniformly to obtain the first solution;

(2) In a nitrogen atmosphere, heat the first solution to 70°C, add 0.1g of benzoyl peroxide, react for 4 hours, add 0.05g of benzoyl peroxide, continue the reaction for 4h, and obtain the second solution .

(3) After the second solution is cooled to 20°C, the fluoropolymer is precipitated with methanol, dried under reduced pressure, and the prepared coating composition is dissolved with HFE-458.

Example 4:

(1) 6g of (N-methylperfluorobutanesulfonamido)ethyl acrylate (C4SA), 3g of cetyl methacrylate, 0.4g of 1-propenyloxy-4-hydroxyanthraquinone-9,10 - Diketone (AHD), 0.2g KH570 and 20g HFE-458 were added to a three-necked flask and mixed uniformly to obtain the first solution;

(2) In a nitrogen atmosphere, heat the first solution to 75°C, add 0.05g of benzoyl peroxide, react for 3 hours, add 0.1g of benzoyl peroxide, continue the reaction for 5h, and obtain the second solution .

(3) After the second solution is cooled to 10°C, the fluoropolymer is precipitated with methanol, dried under reduced pressure, and the prepared coating composition is dissolved with HFE-458.

Example 5:

(1) Add 9g of (N-methylperfluorohexanesulfonamido) ethyl methacrylate (C6SMA), 0.1g of norbornyl acrylate, 0.005g of 1,8-naphthalimide acrylate, 0.3g KH570 and 25g 1H, 1H-pentafluoropropanol were added into a three-necked flask, and mixed uniformly to obtain the first solution;

(2) In a nitrogen atmosphere, heat the first solution to 80°C, add 0.03g of azobisisobutyronitrile, react for 2 hours, add 0.15g of azobisisobutyronitrile, continue the reaction for 6h, and obtain the second Second solution.

(3) After the second solution is cooled to 10° C., the fluoropolymer is precipitated with methanol, dried under reduced pressure, and the prepared coating composition is dissolved with 1H,1H-pentafluoropropanol.

Embodiment 6:

(1) Add 8g of (N-methylperfluorobutanesulfonamido) ethyl methacrylate (C4SMA), 1g of norbornyl acrylate, 0.5g of 1,8-naphthalimide acrylate, 0.5g of KH570 Add 30g of 1H,1H-pentafluoropropanol into a three-necked flask, and mix uniformly to obtain the first solution;

(2) In a nitrogen atmosphere, heat the first solution to 80°C, add 0.01g of azobisisobutyronitrile, react for 2 hours, add 0.2g of azobisisobutyronitrile, continue the reaction for 6h, and obtain the second Second solution.

(3) After the second solution is cooled to 0°C, the fluoropolymer is precipitated with methanol, dried under reduced pressure, and the prepared coating composition is dissolved with 1H,1H-pentafluoropropanol.

Comparative example 1:

Add 9g of octadecyl acrylate and 30g of tetrahydrofuran into a three-neck flask, mix uniformly, heat to 70°C, add 0.1g of azobisisoheptanonitrile, and react for 8 hours. Then dilute it with tetrahydrofuran to prepare a coating composition with a mass fraction of 2%.

Comparative example 2:

Add 9g of (N-methylperfluorohexanesulfonamido)ethyl methacrylate (C6SMA) and 30g of 1H,1H-pentafluoropropanol into a three-necked flask, mix well, heat to 70°C, and add 0.1g Azobisisoheptanonitrile, reacted for 8 hours. Then dilute it with 1H,1H-pentafluoropropanol to prepare a coating composition with a mass fraction of 2%.

Embodiment 1-6 and comparative example 1-2

Use a silicon wafer as the object to be processed for pretreatment, first in an acetone solution for 30 minutes, then clean it with HFE7200 and dry it.

The pretreated silicon wafer was dipped in the coating solution with a mass fraction of 2% prepared in Example 1-6, taken out after dipping for 10s, and dried in the atmosphere for 5min to obtain a test piece.

Performance Testing

Test Methods:

(1) Static contact angle of water

The contact angle test adopts the CAM200 surface tension and contact angle tester produced by Finland KSV company. The measurement type is static water contact angle, and the droplet size is 3 μL. The obtained contact angle data is based on the contact angle of four different points on the sample surface. average value.

(2) Rolling contact angle of water

Put the test piece on a sample stage, and constantly adjust the inclination angle of the sample stage so that the 50 μL water drop just rolls. At this time, the angle at which the sample stage is tilted is the rolling contact angle.

(3) Static contact angle of oil

The contact angle test adopts the CAM200 surface tension and contact angle tester produced by KSV Company of Finland. The test is the static contact angle of n-hexadecane. The droplet size is 3 μL. The obtained contact angle data is based on four different points on the sample surface. The average value of the contact angle.

(4) Fluorescence visibility performance

The fluorescence visibility was irradiated with a SPECTROLINE FC-100 ultraviolet lamp, observed, and the fluorescence visibility was evaluated in three stages: ● (strong), ◎ (weak), and ○ (none).

The test results are as follows:

The static contact angle test result of each example gained coating of table 1

It can be seen from the above table that the static water contact angles of the fluorescent visible electronic protective coatings prepared by the present invention are all above 105°, indicating that they have low surface energy and good fluorescent visibility. Figure 1 is the water contact angle diagram of Example 5 (left) and Comparative Example 1 (right), it can be seen that compared with common acrylic paints, this paint composition has a better hydrophobic effect.

Claims (10)

1. a kind of fluorescent visual type electronic protection coating composition, it is characterised in that it includes the fluorine-containing propene of 40-90 parts by weight Acid ester monomer, the non-fluoroacrylate monomers of 1-50 parts by weight, the fluorescent monomer of 0.01-5 parts by weight, the silicon of 0.1-5 parts by weight Alkane coupling agent.

2. composition according to claim 1, it is characterised in that the general structure of the fluorinated acrylate monomer is：

In formula (1), X is main chain side base, selected from hydrogen atom, halogen atom, cyano group, phenyl, substituted-phenyl, alkyl or alkyl halide Base；Y is linking group, can be fatty group, aromatic series base, the fatty group containing oxygen atom, the aromatic series base containing oxygen atom, Fatty group containing oxygen atom, the aromatic-aliphatic base containing oxygen atom, ester group ,-(CH₂)_m-S-、-(CH₂)_m-SO₂-、-(CH₂)_m- N(OH)-(CH₂)_n- or-(CH₂)_m-N(C_nH_1n+1)-SO₂-, R is fluoro-containing group, is straight or branched fluoroalkyl；

Above-mentioned fluorinated acrylate monomer can one or more be used in mixed way.

3. composition according to claim 2, it is characterised in that the fluorinated acrylate monomer is the short fluorine carbon of environment-friendly type Side chain fluorinated acrylate monomer.

4. composition according to claim 3, it is characterised in that the short fluorocarbon side chains fluorinated acrylate list of environment-friendly type Body by perfluoroethyl hexyl ethyl ester, perfluoroethyl hexyl ethyl ester, acrylic acid (N- methyl perfluoro butane sulfoamido) ethyl ester, One or more in acrylic acid (N- methyl perfluoro hexanes sulfoamido) ethyl ester are mixed by any ratio.

5. composition according to claim 1, it is characterised in that the non-fluorinated monomer is by butyl acrylate, methyl Butyl acrylate, Hexyl 2-propenoate, hexyl methacrylate, n-octyl, n octyl methacrylate, acrylic acid are different pungent Ester, EHMA, dodecyl acrylate, lauryl methacrylate, Process Conditions of Cetane Acrylate, methacrylic acid 16 Ester, octadecyl acrylate, octadecyl methacrylate, adamantyl acrylate, norborny acrylate, isobornyl third One or more in olefin(e) acid ester, bicyclopentyl acrylate and cyclohexylacrylic ester are mixed by any ratio.

6. composition according to claim 1, it is characterised in that the fluorescent monomer is by the virtue containing polymerizable carbon-carbon double bond Fragrant condensed cyclic structure fluorescent monomer, the conjugated structure fluorescent monomer containing polymerizable carbon-carbon double bond, the metal containing polymerizable carbon-carbon double bond The one or more in fluorescent monomer are coordinated to be mixed by any ratio.

7. composition according to claim 1, it is characterised in that the fluorescent monomer is glimmering by polymerizable carbon-carbon double bond stilbene class Light monomer, polymerizable carbon-carbon double bond pyrene class fluorescent monomer, polymerizable carbon-carbon double bond indoles fluorescent monomer, polymerizable carbon-carbon double bond Benzoxazoles class fluorescent monomer, polymerizable carbon-carbon double bond quinolines fluorescent monomer, polymerizable carbon-carbon double bond carbazoles fluorescent monomer, Polymerizable carbon-carbon double bond naphthalimide fluorescent monomer, polymerizable carbon-carbon double bond Coumarins fluorescent monomer, polymerizable carbon carbon are double Key pyrazolines fluorescent monomer, polymerizable carbon-carbon double bond Anthraquinones fluorescent monomer, polymerizable carbon-carbon double bond rhodamine fluorescence list One or more in body are mixed by any ratio.

8. composition according to claim 1, it is characterised in that the general formula R of the silane coupler₁SiX₁X₂X₃, in formula R₁For sulfydryl, mercapto alkyl, vinyl or (methyl) acryloxy；X₁、X₂And X₃Selected from alkyl, alkoxy, aryloxy group or Acyl group, wherein X₁、X₂And at least one in Xx is alkoxy, aryloxy group or acyl group.

9. a kind of preparation method of fluorescent visual type electronic protection coating composition, it is characterised in that the preparation method is included such as Lower step：

(1) by the fluorinated acrylate monomer of 40-90 parts by weight, the non-fluoroacrylate monomers of 1-50 parts by weight, 0.01-5 weights The fluorine series solvent for measuring the fluorescent monomer of part, 0.1-5 parts by weight silane coupler and 200-300 parts by weight uniformly mixes in container Close, obtain the first solution；

(2) in nitrogen atmosphere, the first solution is heated to 60 DEG C -80 DEG C, and adds the initiator of 0.1-2 parts by weight, is incubated 2-6 hour, the initiator of 0.1-2 parts by weight is added, continue to react 2-6h, obtain the second solution；

(3) treat that the second solution is cooled to 0-40 DEG C, separate out fluoropolymer using methanol, be dried under reduced pressure, and use fluorine series solvent Dissolve the coating composition being configured to.

10. preparation method according to claim 9, it is characterised in that the fluorine series solvent by perfluoro acetone, perfluor oneself Ketone, perfluoroalkyl acid, hydrofluoroether, perfluoro alkane, hydrofluoroalkane, hydrogen chlorofluoro-alkane, full chlorofluoro-alkane, perfluor trialkylamine, hydrogen One or more in fluorine alcohol, phenyl-hexafluoride, hexafluoro toluene, hexafluoro meta-xylene or perfluoroalkyl ethers are mixed by any ratio.