CN114921165B

CN114921165B - Hand feeling paint and preparation method and application thereof

Info

Publication number: CN114921165B
Application number: CN202210599421.5A
Authority: CN
Inventors: 王跃健; 汪文笔; 符饶生; 孙润鹤
Original assignee: Hunan Sokan New Materials Co ltd
Current assignee: Matsui (Shanghai) New Materials Research Institute Co.,Ltd.
Priority date: 2022-05-30
Filing date: 2022-05-30
Publication date: 2023-03-24
Anticipated expiration: 2042-05-30
Also published as: CN114921165A

Abstract

The invention discloses a hand feeling paint and a preparation method and application thereof, belonging to the technical field of paints. The preparation raw materials of the hand feeling paint comprise a component A and a component B; the component A comprises the following preparation raw materials: microcapsule modified polyurethane polymer, organic silicon modified polyester polyol resin, linear polyester polyol resin, elastic handfeel agent, anti-fouling auxiliary agent and elastic repair powder; the component B comprises the following preparation raw materials: isocyanate and a solvent. The hand feeling paint combines the soft and thick elastic hand feeling of PU elastic rubber paint, excellent performance and anti-back tack; the excellent flexibility and adhesive force suitable for the TPU soft rubber are also kept; meanwhile, the antifouling paint has good antifouling property, and the surface has no obvious trace after an antifouling test; the scratch self-repairing function of special beads is achieved, and the scratch self-repairing function can be achieved in a short time at room temperature.

Description

Hand feeling paint and preparation method and application thereof

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to a hand feeling paint and a preparation method and application thereof.

Background

Along with the improvement of living standard and the progress of artificial intelligent electronic equipment, intelligent electronic products such as mobile phones and intelligent watches are more and more widely applied, people pursue more and more high appearance of the products, and meanwhile, the matching equipment for wearing the electronic equipment is more and more comprehensive, so that an electronic equipment protective sleeve made of TPU soft rubber materials and a soft rubber wearing strip made of TPU materials are born, the appearance of the products made of the TPU materials per se is poor in dirt resistance, and in addition, the products per se have the appearance protection effect on electric equipment, and are very easy to stain and scratch, PU rubber paint in the related technology is thick in hand feeling, but the dirt resistance is very poor, particularly color matching is very easy to stick dirt and black, cannot be cleanly wiped and is very unattractive; and the protective shell is a protective shell, so that the protective shell can be frequently collided with hard dust to scrape and cannot be self-repaired, namely, the attractive appearance of the product is greatly influenced by the scratch of the shell, and the service life of the product is greatly shortened.

Therefore, a feeling paint which has a good self-repairing effect is required to be developed.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the hand feeling paint which has good self-repairing effect.

The invention also provides a preparation method of the hand feeling paint.

The invention also provides application of the hand feeling paint.

The method comprises the following specific steps: the invention provides a hand feeling paint, which comprises a preparation raw material A and a preparation raw material B;

the component A comprises the following preparation raw materials: 25-45 parts of microcapsule modified polyamino acid polymer, 10-20 parts of organic silicon modified polyester polyol resin, 10-20 parts of linear polyester polyol resin, 1-3 parts of elastic handfeel agent, 2-4 parts of anti-fouling assistant and 6-10 parts of elastic repair powder;

the component B comprises the following preparation raw materials: isocyanate and a solvent.

According to one of the technical schemes of the hand feeling paint, the invention at least has the following beneficial effects:

in the hand feeling paint, the component A plays a role of a main agent, and the component B plays a role of curing; and mixing the component A and the component B, adjusting the viscosity, and then crosslinking and curing to obtain a paint film.

The hand feeling paint provided by the invention utilizes the microcapsule modified polyurethane polymer, and the microcapsule modified polyurethane polymer has the advantages of good tensile flexibility, outstanding elastic self-repairing function, and good anti-fouling capability and smooth hand feeling.

The organic silicon modified polyester polyol resin has good soft hand feeling, good adhesion effect on TPU materials and outstanding flexibility; meanwhile, the organic silicon modified polyester polyol resin is selected, so that the antifouling paint has more excellent and more durable antifouling property.

The linear polyester polyol resin has excellent weather resistance, excellent wear resistance, soft rubber inner thick hand feeling and excellent flexibility.

The elastic repairing powder has certain dullness, simultaneously greatly enhances the resilience and self-repairability of a coating prepared from the hand-feeling paint, and also enhances the stain resistance of the surface.

The anti-fouling auxiliary agent is used for further improving the anti-fouling capability of the paint film.

Isocyanate is used as a curing agent, so that a paint film is cured into a film. Adding a solvent into the component B to control the viscosity of the component B, and utilizing the construction; and simultaneously, the dispersion effect of the component B in the component A is improved.

According to the invention, through the synergistic collocation of the preparation raw materials, the hand feeling paint with a beneficial self-repairing effect is finally prepared.

According to some embodiments of the invention, the a component comprises the following preparation starting materials: 25 to 45 portions of microcapsule modified polyamino acid polymer, 10 to 20 portions of organic silicon modified polyester polyol resin, 10 to 20 portions of linear polyester polyol resin, 1 to 3 portions of elastic hand feeling agent, 2 to 4 portions of anti-pollution auxiliary agent, 20 to 35 portions of diluent, 6 to 10 portions of elastic repair powder, 0.1 to 0.5 portion of drier and 0.2 to 0.5 portion of flatting agent.

The addition of the diluent is convenient for production, the diluent is not added, the viscosity is too high, and the production and dispersion are not facilitated; meanwhile, the diluent is used for dissolving other additives (an elastic hand feeling agent, an anti-fouling additive, elastic repairing powder, a drier and a flatting agent) in the component A and then is added into the formula, so that the dispersion and the dissolution of the other additives in the component A are facilitated.

The drier mainly improves the reaction activity and shortens the baking time; excessive addition of siccatives can result in short paint pot life.

The leveling agent is added to promote surface leveling and prevent defects such as shrinkage cavity, oil vortex and the like.

According to some embodiments of the invention, the B component comprises the following preparation raw materials in parts by weight: 70-80 parts of isocyanate and 20-30 parts of solvent.

The control of the curing of the hand-feel paint is realized by controlling the using amount of the isocyanate.

According to some embodiments of the invention, the isocyanate is hexamethylene diisocyanate trimer.

The hexamethylene diisocyanate trimer has good reaction activity, so that the curing efficiency of the hand feeling paint is improved.

According to some embodiments of the invention, the weight ratio of the a-component to the B-component is 100:30 to 35.

According to some embodiments of the invention, the solid content of the microcapsule-modified polyurethane polymer is 50% to 60%.

According to some embodiments of the invention, the viscosity of the microcapsule-modified polyamino acid polymer is 1600cps/25 to 4000cps/25 ℃. The viscosity is moderate, and the construction is facilitated. According to some embodiments of the invention, the acid value of the microcapsule-modified polyurethane polymer is 2mg KOH/g to 5mg KOH/g.

According to some embodiments of the invention, the microcapsule-modified polyurethane polymer has a hydroxyl value of 125mg KOH/g to 135mg KOH/g. The hydroxyl value is controlled in the range, the polymer has high reactivity, and the cured surface of the paint film has high crosslinking density.

By controlling the parameters of the microcapsule modified polyamino acid polymer, the modified polyamino acid polymer has good scratch resistance and weather resistance and quick repair effect.

According to some embodiments of the invention, the microcapsules are microcapsules impregnated with a healing agent.

The microcapsules injected with the repairing agent are compounded on the polyamino acid polymer together under the action of the catalyst to form the modified polyamino acid polymer with the self-repairing function.

According to some embodiments of the invention, the microcapsule-modified poly-amino acid polymer is L-2960 of Cherokee.

According to some embodiments of the invention, the silicone-modified polyester polyol resin has a solids content of 78% to 82%.

According to some embodiments of the invention, the silicone-modified polyester polyol resin has a viscosity of 1200cps/25 to 1800cps/25 ℃. The viscosity is moderate, and the construction is facilitated.

According to some embodiments of the invention, the organic silicon modified polyester polyol resin has an acid value of 2mg KOH/g to 3mg KOH/g.

According to some embodiments of the invention, the hydroxyl value of the silicone-modified polyester polyol resin is from 210mg KOH/g to 250mg KOH/g. The hydroxyl value is controlled in the range, the reactivity of the resin is high, and the crosslinking density of the cured surface of a paint film is high.

The organic silicon modified polyester polyol resin has good soft hand feeling and good adhesion to TPU materials, and organic silicon modified groups are embedded in a polyester polyol chain after organic silicon modification, so that the polyester polyol polymer has excellent dirt resistance.

According to some embodiments of the invention, the silicone-modified polyester polyol resin is PU-583 of zhongshanjieda.

According to some embodiments of the invention, the linear polyester polyol resin has a solids content of 78% to 82%.

According to some embodiments of the present invention, the linear polyester polyol resin has a viscosity of 2600cps/25 to 3400cps/25 ℃. The viscosity is moderate, and the construction is facilitated.

According to some embodiments of the invention, the linear polyester polyol resin has an acid value of 1mg KOH/g to 3mg KOH/g.

According to some embodiments of the invention, the hydroxyl value of the linear polyester polyol resin is from 105mg KOH/g to 120mg KOH/g. The hydroxyl value is controlled in the range, the reactivity of the resin is high, and the crosslinking density of the cured surface of a paint film is high.

According to some embodiments of the invention, the linear polyester polyol resin is kostew

670BA。

According to some embodiments of the invention, the elastic feel agent is a modified silicone high molecular polymer.

The addition of the modified organic silicon high molecular polymer to the coating can greatly improve the thick feeling and the rubber elastic feeling of the chiral paint.

According to some embodiments of the invention, the modified silicone high molecular polymer is polyether modified polysiloxane.

The hand feeling auxiliary agent component is polyether modified polysiloxane, the cohesive energy density of molecules is low, the intermolecular acting force is small, the surface energy of the molecules is low, and the hand feeling auxiliary agent component has excellent wetting dispersibility and smooth feeling; the polyether modified polysiloxane has a large molecular weight, and the inner rotation of ether bonds and the like show excellent flexibility; can enhance the smooth feeling and the thick feeling of the elastic hand feeling paint.

According to some embodiments of the invention, the elastic feel agent is TS-50 of the memento chemical industry.

According to some embodiments of the invention, the anti-fouling aid is a hydroxyl-bearing silicone-modified polyacrylate.

The hydroxyl groups carried by the polymer of the organosilicon modified polyacrylate with hydroxyl groups can participate in the polymerization reaction of the chiral paint (the hydroxyl groups in the main resin and the isocyanate in the component B), so that the antifouling effect is more durable.

According to some embodiments of the invention, the anti-soil additive is available from DSP-3890 of Jettida.

According to some embodiments of the invention, the diluent comprises ethyl acetate, butyl acetate and diacetone alcohol (CAS number 123-42-2).

According to some embodiments of the invention, the elastic restoring powder is spherical silicon-modified polyurethane microparticles.

The elastic repairing powder has excellent smoothness due to the silicon modified structure; because the spherical silicon is spherical particles, the spherical silicon has better rebound resilience and toughness; meanwhile, the extinction powder has the same extinction effect as the extinction powder.

According to some embodiments of the invention, the elastic healing powder is RS-D80-4 of rockwell.

According to some embodiments of the invention, the drier is a dibutyltin dilaurate mixture.

According to some embodiments of the invention, the leveling agent is an organosilicon modified leveling agent.

According to some embodiments of the invention, the solvent is butyl acetate.

According to some embodiments of the invention, the raw materials for preparing the feel paint further comprise a component C.

The component C is used for adjusting the construction viscosity of the hand feeling paint.

According to some embodiments of the invention, the weight ratio of the a component, the B component and the C component is 100:30 to 35:30 to 50.

By controlling the weight ratio of the components, the construction viscosity of the hand feeling paint is moderate, and the A component and the B component are completely cured.

According to some embodiments of the invention, the C component comprises at least one of ethyl acetate, butyl acetate and diacetone alcohol.

According to some embodiments of the invention, the feel paint has a viscosity of 10.5s to 12s (NK-2 cup).

The invention provides a preparation method of the hand feeling paint, which comprises the following steps: and mixing the component A and the component B and adjusting the viscosity.

According to some embodiments of the invention, the adjusted viscosity is adjusted by the C-component.

According to some embodiments of the invention, the method of making the feel paint comprises the steps of: mixing the A component, the B component and the C component.

According to some embodiments of the invention, the method of preparing the a-component comprises the steps of:

s1, mixing the microcapsule modified polyurethane polymer, the organic silicon modified polyester polyol resin, the linear polyester polyol resin and part of the diluent; preparing a first mixture;

s2, mixing the first mixture, the elastic repairing powder and part of the diluent to prepare a second mixture;

s3, mixing the anti-fouling auxiliary agent, the flatting agent, the elastic handfeel agent, the second mixture and part of the diluent to prepare a third mixture;

s4, mixing the drier, the third mixture and the rest of the diluent.

According to some embodiments of the invention, the method of preparing the B-component comprises: the method comprises the following steps: and mixing the isocyanate and the solvent, and stirring and dispersing for 10-15 min to obtain the component B.

In a third aspect, the invention provides a hand feeling paint coating, which is prepared from the hand feeling paint.

The invention provides a preparation method of the hand feeling paint coating, which comprises the following steps: and spraying the hand feeling paint on the surface of the base material, and drying.

According to some embodiments of the invention, the sprayed film has a thickness of 35 μm to 45 μm.

According to some embodiments of the invention, the temperature of the drying is 75 ℃ to 85 ℃.

According to some embodiments of the invention, the drying time is 45min to 60min.

According to some embodiments of the invention, the substrate is a TPU (Thermoplastic polyurethane elastomer) substrate.

In a fifth aspect, the invention provides the use of the hand paint in the preparation of a protective shell.

According to some embodiments of the invention, the protective shell is a TPU soft gel protective shell of the electronic device.

According to some embodiments of the invention, the TPU soft gum protection shell of the electronic device comprises a TPU soft gum protection shell of a smart phone or a TPU soft gum protection shell of a smart wearable device.

According to some embodiments of the invention, the application comprises the steps of: and spraying the hand feeling paint on the shell of the protective shell, and drying.

Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

Detailed Description

The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.

In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

Specific examples of the present invention are described in detail below.

In the embodiment of the invention, the microcapsule modified poly-amino acid polymer is purchased from L-2960 of Cherokee road, the solid content of the polymer is 55%, the viscosity is 1600 cps/25-4000 cps/25 ℃, the acid value is 2mg KOH/g-5 mg KOH/g, and the hydroxyl value is 130mg KOH/g.

The polymer is specially modified by a microcapsule self-repairing composite material, about 20 percent of ionomer with opposite charges is added into the polymer, and a polymer network or an interpenetrating network structure can be formed by depending on the interaction between charged groups, so that the physical properties required by a coating film can be obtained, acting force can be lost (disordering) at a certain temperature, the network is formed again, and the aim of repairing is fulfilled; the paint has good scratch resistance, weather resistance and self-repairing effect.

In the embodiment of the invention, the organic silicon modified polyester polyol resin is purchased from PU-583 of Zhongshanjieda, the solid content is 80%, the viscosity is 1000 cps/25-1500 cps/25 ℃, the acid value is 2mg KOH/g-3 mg KOH/g, and the hydroxyl value is 230mg KOH/g.

The resin has good soft hand feeling, excellent adhesion effect on TPU materials and outstanding flexibility; meanwhile, the organic silicon is used for modification, so that the antifouling paint has more excellent and more durable antifouling property.

The resin is prepared by reacting active group-hydroxyl on a polymer chain with an organosilicon intermediate. In order to prevent the gel phenomenon, the hydroxyl of the organosilicon intermediate is methylated, and then the organosilicon modified polyester polyol resin is obtained by reacting the hydroxyl with organosilicon hydroxyl with the hydroxyl on the polymer under the action of a catalyst. The reaction equation is as follows:

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in the embodiment of the invention, the linear polyester polyol resin is purchased from Corsia

670BA, the solid content of the compound is 80 percent, the viscosity is 260 cps/25-3400 cps/25 ℃, the acid value is 1mg KOH/g-3 mg KOH/g, the hydroxyl value is 120mg KOH/g, and the resin has excellent weather resistance, excellent wear resistance, soft rubber thick hand feeling and flexibility.

In the embodiment of the invention, the elastic feeling agent is obtained from TS-50 in Meyer chemical engineering, is a modified organic silicon high molecular polymer (polyether modified polymethyl siloxane copolymer), and can greatly improve the thick feeling and rubber elastic feeling of the elastic paint when added into the coating.

In the embodiment of the invention, the anti-fouling auxiliary agent is purchased from DSP-3890 of Jettida, and is organic silicon modified polyacrylate with hydroxyl, and the hydroxyl carried by the polymer can participate in the polymerization reaction of the coating, thereby ensuring that the anti-fouling effect is more durable.

In the embodiment of the invention, the diluent is a mixed solvent of ethyl acetate, butyl acetate and diacetone alcohol, which is commercially available and analytically pure.

In the embodiment of the invention, the elastic repairing powder is RS-D80-4 from Roxter and is spherical silicon modified polyurethane particles. Due to the silicon modified structure, the silicon modified silicone rubber has excellent smoothness; due to the spherical structure, the spherical rubber has better rebound resilience and toughness, and meanwhile, the powdery particles have a certain extinction effect;

in an embodiment of the invention, the drier is a compound available as T-12 from gas company, USA, and the compound is dibutyltin dilaurate.

In the embodiment of the invention, the leveling agent is purchased from BYK333 of Bike Germany and is an organic silicon modified leveling agent.

In an embodiment of the present invention, the hexamethylene diisocyanate trimer curing agent is available from Bayer, germany

N3390, the NCO content of the compound is 19.6% + -0.3%, the solid content is 90% + -1%, the compatibility is good, the chemical resistance and the weather resistance are excellent, the gloss retention is excellent, and the mechanical property is excellent.

The preparation method of the hand feeling paint in the embodiment of the invention comprises the following steps:

adjusting the component A, the component B and the diluent to proper viscosity according to a certain weight ratio to obtain the hand feeling paint; wherein the component A comprises: and B component: the weight ratio of the diluent is 100:30 to 35:30 to 50.

The viscosity of the hand feeling paint is 10.5 s-12 s (NK-2 cup).

The preparation method of the hand feeling paint coating in the embodiment of the invention comprises the following steps:

spraying the hand feeling paint on the surface of a TPU soft rubber base material of the electronic wearable equipment, and drying to obtain a hand feeling paint coating; the thickness of the sprayed film is 35-45 μm, the drying temperature is 75-80 ℃, and the drying time is 45-60 min.

The preparation method of the component A comprises the following steps: the method comprises the following steps:

s1, washing a stirring production container with ethyl butyrate;

s2, adding the microcapsule modified polyurethane polymer, the organic silicon modified polyester polyol resin and the linear polyester polyol resin into a production container, and stirring for 15-20 min at a stirring speed of 500-800 r/min;

s3, uniformly stirring 1/4 of the diluent by weight, adding the mixture into a production container, and stirring for 10-15 min at a stirring speed of 300-500 r/min;

s4, adding the elastic repairing powder while stirring, wherein the stirring speed is 300-500 r/min; after the elastic repairing powder is completely dissolved in the resin and the diluent, dispersing at a high speed for 15-20 min, wherein the stirring speed is 500-800 r/min;

s5, uniformly stirring the flatting agent, the anti-fouling auxiliary agent, the elastic handfeel agent and 1/4 of the diluent by weight, adding the mixture into a production container, and stirring for 10-15 min at a stirring speed of 300-500 r/min;

s6, uniformly stirring the drier and 1/4 of the diluent by weight, adding the mixture into a production container, and stirring for 10-15 min at a stirring speed of 300-500 r/min;

s7, adding the rest part of the diluent into a production container, and stirring for 10-15 min at a stirring speed of 300-500 r/min;

filtering with 200 mesh filter bag to obtain the component A.

The preparation method of the component B comprises the following steps: the method comprises the following steps:

mixing hexamethylene diisocyanate trimer with a solvent under the condition of keeping constant temperature and humidity indoors, stirring and dispersing for 10-15 min under the condition of filling nitrogen, stirring at the speed of 300-500 r/min, and filtering by using a 300-mesh filter bag after the reaction is finished to obtain the component B.

The nitrogen is filled in the preparation process to prevent the water vapor in the air from reacting with the isocyanate curing agent to lose efficacy.

Example 1

The embodiment is a hand feeling paint which comprises a component A, a component B and a component C, wherein the component A is prepared from preparation raw materials in parts by weight shown in a table 1; the component B consists of preparation raw materials in parts by weight shown in Table 2; the component C consists of the preparation raw materials in parts by weight shown in Table 3.

TABLE 1 parts by weight of ingredients for preparation of the components A

TABLE 2 parts by weight of ingredients for preparation of the components B

B component	Parts by weight
		Hexamethylene diisocyanate trimer	75
Acetic acid butyl ester	25

TABLE 3 parts by weight of ingredients for preparation of the components

C component	Parts by weight
		Acetic acid butyl ester	20
Ethyl acetate	55
		Diacetone alcohol	25

The preparation method of the hand feeling paint comprises the following steps:

100 parts of the component A and 30 parts of the component B are weighed and added to 50 parts of the component C to adjust the viscosity to 12s (NK-2 cup), and the hand feeling paint is obtained.

The hand feeling paint finished product is coated on the surface of a sample (the electronic equipment protective sleeve made of the TPU soft shell material) according to the following method, and subsequent performance tests such as appearance and hand feeling comparison, elastic self-repairing performance, anti-fouling test and the like are carried out.

Spraying the hand feeling paint on the surface of the electronic equipment protective sleeve made of the TPU soft shell material, and drying to obtain a hand feeling paint coating; wherein the thickness of the sprayed film is 40-45 μm, the drying temperature is 80 ℃, and the drying time is 60min.

s1, washing a stirring production container with ethyl butyrate;

s2, adding the microcapsule modified polyurethane polymer, the organic silicon modified polyester polyol resin and the linear polyester polyol resin into a production container, and stirring for 20min at the stirring speed of 800r/min;

s3, uniformly stirring 1/4 of the diluent by weight, adding the diluent into a production container, and stirring for 15min at a stirring speed of 500r/min;

s4, adding the elastic repairing powder into a production container while stirring, wherein the stirring speed is 500r/min; after the extinction powder is completely dissolved in the resin and the diluent, the extinction powder is dispersed at a high speed for 20min, wherein the dispersion speed is 800r/min;

s5, uniformly stirring the flatting agent, the anti-fouling auxiliary agent, the elastic handfeel agent and 1/4 of the diluent by weight, adding the mixture into a production container, and stirring for 15min at a stirring speed of 500r/min;

s6, uniformly stirring the drier and 1/4 of the diluent by weight, adding the mixture into a production container, and stirring for 15min at a stirring speed of 500r/min;

s7, adding the rest part of the diluent into a production container, and stirring for 15min at a stirring speed of 500r/min;

filtering with 200 mesh filter bag to obtain the component A.

the preparation method of the component B comprises the following steps: under the condition of keeping constant temperature and humidity (the temperature is specified to be 22 +/-5 ℃ and the humidity is specified to be 50% +/-2%) indoors, adding hexamethylene diisocyanate trimer in the component B and a solvent into a container according to parts by weight, and stirring and dispersing for 12min under the condition of charging nitrogen at the stirring speed of 600r/min; filtering with 300 mesh filter bag to obtain the component B.

Example 2

The present example is a hand feeling paint, and the difference from example 1 is that: the component A consists of the preparation raw materials in parts by weight shown in Table 4.

TABLE 4 parts by weight of ingredients for preparation of the components A

The preparation method and the coating process are the same as in example 1.

Comparative example 1

The comparative example is a hand paint, and the difference from the example 1 is that: the component A consists of the preparation raw materials in parts by weight shown in Table 5.

TABLE 5 parts by weight of ingredients for preparation of the components A

The preparation method and the coating process are the same as in example 1.

Comparative example 2

The comparative example is a hand paint, and the difference from the example 1 is that: the component A consists of the preparation raw materials in parts by weight shown in Table 6.

TABLE 6 parts by weight of ingredients for preparation of the components A

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The preparation method and the coating process are the same as in example 1.

Comparative example 3

The comparative example is a hand paint, and the difference from example 1 is that: the component A consists of the preparation raw materials in parts by weight shown in Table 7.

TABLE 7 parts by weight of ingredients for preparation of the components A

The preparation method and the coating process are the same as those of the example 1, and the difference is that: the microcapsule modified polyurethane polymer with the mass ratio of 40% in the formula is replaced by special modified PU resin in an equivalent manner, the special modified PU resin is purchased from L-2900 of Cherokee blue, the solid content of the compound is 55%, the viscosity is 1500 cps/25-4000 cps/25 ℃, the acid value is 2mg KOH/g-5 mg KOH/g, and the hydroxyl value is 130mg KOH/g.

Comparative example 4

The comparative example is a hand paint, and the difference from the example 1 is that: the component A consists of the preparation raw materials in parts by weight shown in Table 8.

TABLE 8 parts by weight of ingredients for preparation of the components A

The preparation method and the coating process are the same as those of the example 1, and the difference is that: the equivalent amount of the microcapsule modified polyurethane polymer of 40% mass parts in the formula is changed into the hydroxy acrylic resin. And hydroxy acrylic resins from Stokes

8822F2 is a single-end dihydroxy organic silicon modified hydroxy acrylic resin, has smooth and thick hand feeling and excellent anti-fouling effect, and also has self-repairing function.

Comparative example 5

The comparative example is a hand paint, and the difference from the example 1 is that: the component A consisted of the preparation raw materials in the parts by weight shown in Table 9.

TABLE 9 parts by weight of ingredients for preparation of the components

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The preparation method and the coating process are the same as those of the example 1, and the difference is that: the equivalent amount of 15% by mass of the organosilicon modified polyester polyol resin in the formula is changed into polycarbonate diol resin. The polycarbonate diol resin is purchased from Asahi chemical T-5652, and has excellent scratch resistance and weather resistance, good compatibility and soft hand feeling, and excellent flexibility.

Comparative example 6

The present example is a hand feeling paint, and the difference from example 1 is that: the component A consists of the preparation raw materials in parts by weight shown in Table 10.

TABLE 10 parts by weight of ingredients for preparation of the components

The preparation method and the coating process of the comparative example are the same as those of example 1, with the difference that: the elastic repair powder and the like in the formula are replaced by extinction powder which is purchased from Japanese Tosoh E-1011, so that the product has good transparency, fine hand feeling and excellent performance. Meanwhile, the paint has a good extinction effect, and when the paint is added into a formula, the relative extinction effect is better than that of the elastic repair powder, and the paint can achieve the simultaneous gloss with a small addition amount.

Test example

The coating prepared in the embodiments 1-2 and the comparative examples 1-6 of the invention is sprayed on a TPU soft rubber protective sleeve material, and then the performance is carried out, wherein the specific test items are as follows:

1. and (3) testing the adhesive force:

the surface to be measured is inspected visually, and the appearance is not abnormal. Using a sharp blade (the blade angle is 20-30 degrees, the blade thickness is 0.43 mm)

+/-0.03 mm) scribing 1mm multiplied by 1mm small grids on the surface of the test sample according to the film thickness specification; sticking the NICIBANST 405AP-24 adhesive tape on the tested cell, flattening the adhesive tape on the upper part of the grid area by using the back of a nail, and standing for 90s +/-30 s; one end of the tape was grasped by hand and quickly pulled off in the opposite 60 ° direction. The paint coating was checked for flaking off (cf. GB/T9286-2021).

2. Gloss:

and measuring the surface gloss of the TPU soft rubber protective sleeve material coated with the hand feeling paint by using a micro triangular gloss meter at an angle of 60 degrees. The gloss value is between 4.5 and 5.0.

3. RCA paper tape friction:

installing and fixing the sample by using a NORMAN RCA wear-resisting tester (model: 7-IBB), keeping the sample parallel to a horizontal plane, and adjusting a balance rod to ensure that the gravity pressed on the surface of the paint coating is just 175g; and (4) rubbing to 100 circles, and determining that the coating is not worn out.

4. The surface hand feeling of the coating is as follows:

and (3) touching with hands, evaluating the smoothness and the thick feeling of the paint film, and grading 1-5 according to the quality of the hand feeling, wherein the grade 5 is optimal and the grade 1 is worst.

5. And (3) anti-fouling test:

checking that the TPU soft rubber protective sleeve material coated with the hand feeling paint has no abnormal appearance, no discoloration, bubbles, cracks, falling off and the like, and wiping the surface clean by using dust-free cloth; using a ZEBRA black oily pen to ensure that the oily pen forms an angle of about 90 degrees with the surface of the coating, and applying 1N-2N force to draw 5 handwriting with the thickness of 5 mm-10 mm on the surface of the coating at a constant speed; after standing at normal temperature (about 25 ℃) for 10min, immediately wiping the surface with alcohol (the concentration is more than or equal to 99.5%) (wiping the surface with alcohol-dipped dust-free cloth and applying 5N-8N force for 20 reciprocating motions), and checking the appearance of the product.

6. Limit boil test:

checking that the TPU soft rubber protective sleeve material coated with the hand feeling paint has no abnormal appearance, no discoloration, bubbles, cracks, falling off and the like, and wiping the surface clean by using dust-free cloth; adding purified water into a water bath kettle, and heating to 99 +/-1 ℃; completely immersing a test sample (TPU soft rubber protective sleeve material coated with hand feeling paint) into hot water, and testing time: taking out after the water boiling test for a specified time, and standing for 2 hours at normal temperature (about 25 ℃); and (5) checking the coating surface of the test sample for abnormities such as re-adhesion, bubbling and paint film softening, and carrying out adhesion test on the plastic spraying surface. The product surface appearance is not abnormal, and is judged to be OK when the adhesive force is more than 4B.

7. And (3) bending test:

and folding the head and the tail of the TPU soft rubber protective sleeve material (the specification: 15mm in length, 22mm in width and 3mm in thickness) coated with the hand feeling paint for 180 degrees, repeatedly extruding for 5 times, and observing whether the surface coating cracks or not, and the abnormal problems of the paint film such as paint film arching and the like.

8. Self-repairability test:

and (3) coating the TPU soft rubber protective sleeve material with the hand feeling paint with the weight of about 500g by using a copper brush in a laboratory kept at the room temperature of 25 ℃, brushing back and forth for 10 times, standing for 30 seconds, then seeing the recovery condition of the test mark, and judging OK without obvious scratches and color difference.

The results of the performance tests of the touch paints of examples 1 to 2 of the present invention and comparative examples 1 to 6 are shown in tables 11 to 12.

TABLE 11 partial Performance test results for the feel paints of inventive examples 1-2 and comparative examples 1-6

TABLE 12 partial Performance test results for the hand paints in inventive examples 1 to 4 and comparative examples 1 to 4

From tables 11 to 12, it is known that the tests of the examples 1 and 2 can meet the test requirements, the adhesion performance is OK, the RCA abrasion resistance can meet the standards, the paint film is not worn out for 100 times, the example 1 can reach 180 times, the RCA resistance performance of the example 2 is better, the RCA resistance performance can reach 200 times, the surface hand feeling is better, the anti-fouling test is OK, the extreme water boiling appearance is not abnormal, the adhesion test is also OK, and meanwhile, the bending test paint film is not cracked, arched paint and other abnormalities; and the self-repairing test is also OK, and basically no obvious mark is left after 30 seconds (the difference between the example 1 and the example 2 is that the amount of the microcapsule modified polyurethane polymer is reduced and the amount of the organic silicon modified polyester polyol resin is increased).

The difference between comparative example 1 and example 1 is that: the amount of the microcapsule modified polyurethane polymer in the formula is reduced, and the amount of the organic silicon modified polyester polyol resin is increased. The test results are: the adhesion performance is OK, RCA is wear-resistant for 100 times, the paint film is not worn out, the adhesion performance can reach 230 times, the surface hand feeling is good, the anti-fouling test is OK, the extreme poaching appearance is not abnormal, the adhesion test is also OK, but the surface has slight crack abnormality after the bending test, the self-repairing test is slightly poor, a relatively obvious trace is still basically formed after 30 seconds, and no obvious trace is formed after 60 seconds.

The difference between comparative example 2 and example 1 is that: the amount of the modified polyurethane polymer of the microcapsule is reduced, and the amount of the linear polyester polyol resin is increased. The test results are as follows: the adhesion performance is OK, RCA is wear-resistant for 100 times, the paint film is not worn out, the number of times can reach 120, the surface hand feeling is good, the extreme poaching appearance is not abnormal, the adhesion test is also OK, meanwhile, the paint film is not cracked, arched and the like in the bending test, but the anti-fouling test is slightly poor, the paint film has obvious traces after being wiped, the self-repairing test is also poor, the paint film has obvious scratches within 30 seconds, and the paint film can not be repaired after being placed for 5 minutes.

Comparative example 3, adhesion performance is OK, RCA wear-resisting 100 does not wear through the paint film, can reach 150 times, the surface hand feel is slightly worse, the anti-fouling test is OK, the extreme poaching appearance is not abnormal, the adhesion test is also OK, meanwhile, the bending test paint film has no crack, paint arching and other abnormalities, but the recovery speed is slow, 30 seconds have obvious scratches, and no obvious scratches are left after 60 seconds.

Comparative example 4, the adhesion performance is OK, RCA wear-resisting 100 does not wear through the paint film, can reach 180 times, the surface feel is better, the anti-fouling test is OK, the extreme poaching appearance is not abnormal, the adhesion test is also OK, meanwhile, the bending test paint film has no crack, paint arching and other abnormalities, but the recovery speed is slow, obvious scratches can be found in 30 seconds, and no obvious scratches can be found in the repair after the paint film is placed for 5 minutes.

Comparative example 5, adhesion performance is OK, RCA wear-resistant 100 does not wear through the paint film, can reach 150 times, surface hand feeling is good, anti-fouling test is NG, more obvious trace remains on the surface, extreme poaching appearance is not abnormal, adhesion test is also OK, meanwhile, bending test paint film has no crack, paint arching and other abnormalities, but recovery speed is slow, 30 seconds have obvious scratch, and 60 seconds later have no obvious scratch.

Compared with the comparative example 6, the adhesive force is OK, the RCA wear-resistant 100 paint film is not worn, the adhesive force can reach 180 times, the surface hand feeling is good, the anti-fouling test is NG, obvious traces are remained on the surface, the extreme poaching appearance is not abnormal, the adhesive force test is OK, meanwhile, the bending test paint film is not cracked, arched paint and other abnormalities, the self-repairing test is poor, obvious scratches are formed in 30 seconds, and the paint film cannot be repaired after being placed for 5 minutes.

Within a certain range, the more the dosage of the microcapsule modified poly-amino acid polymer is, the better the self-repairing effect is, and the worse the self-repairing effect is. The more the amount of the organosilicon modified polyester polyol resin is, the better the antifouling and wear resistance is, but the greater the hardness of the paint film is, the better the bending resistance of the paint film is. The linear polyester polyol resin feels best to the touch but the less stain resistance will be.

The common extinction powder only has extinction effect and does not have self-repairing function.

In conclusion, the handfeel paint provided by the invention utilizes the microcapsule modified polyurethane polymer and the special molecular structure and performance to provide excellent self-repairing property and stain resistance of the coating; the organic silicon modified polyester polyol resin has better soft hand feeling, and has more outstanding flexibility in the adhesive force of TPU material; meanwhile, the organic silicon modified antifouling paint has more excellent and more lasting antifouling property; the linear polyester polyol resin has excellent weather resistance, wear resistance, soft rubber thick hand feeling and flexibility; the antifouling auxiliary agent-organic silicon modified polyacrylate with hydroxyl can participate in the polymerization reaction of the coating, so that the antifouling effect of the paint film is more durable. In particular, the elastic repairing powder can provide good anti-fouling capability for the coating and can enable the coating to have better rebound resilience and toughness.

While the embodiments of the present invention have been described in detail with reference to the specific embodiments, the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims

1. A hand feeling paint is characterized in that: the preparation raw materials comprise a component A and a component B;

the component A comprises the following preparation raw materials in parts by weight: 25-45 parts of microcapsule modified polyurethane polymer, 10-20 parts of organic silicon modified polyester polyol resin, 10-20 parts of linear polyester polyol resin, 1-3 parts of elastic handfeel agent, 2-4 parts of anti-fouling assistant and 6-10 parts of elastic repair powder;

the component B comprises the following preparation raw materials: an isocyanate and a solvent;

the microcapsule modified poly-amino acid polymer is lithochol L-2960;

the elastic repairing powder is spherical silicon modified polyurethane particles.

2. The feel paint of claim 1, characterized in that: the component B comprises the following preparation raw materials in parts by weight: 70-80 parts of isocyanate and 20-30 parts of solvent.

3. The feel paint of claim 1, characterized in that: the weight ratio of the component A to the component B is 100:30 to 35.

4. The feel paint according to claim 1 or 2, characterized in that: the solid content of the microcapsule modified polyamino acid polymer is 50% -65%.

5. The feel paint according to claim 1 or 2, characterized in that: the viscosity of the microcapsule modified polyamino acid polymer is 1500 cps/25-5000 cps/25 ℃.

6. The feel paint according to claim 1 or 2, characterized in that: the acid value of the microcapsule modified poly-amino acid polymer is 2-5 mg KOH/g.

7. The feel paint according to claim 1 or 2, characterized in that: the hydroxyl value of the microcapsule modified poly-amino acid polymer is 100-150 mg KOH/g.

8. The feel paint according to claim 1 or 2, characterized in that: the solid content of the organic silicon modified polyester polyol resin is 75-85%.

9. The feel paint according to claim 1 or 2, characterized in that: the viscosity of the organic silicon modified polyester polyol resin is 1000 cps/25-2000 cps/25 ℃.

10. The feel paint according to claim 1 or 2, characterized in that: the acid value of the organic silicon modified polyester polyol resin is 2-5 mg KOH/g.

11. The feel paint according to claim 1 or 2, characterized in that: the hydroxyl value of the organic silicon modified polyester polyol resin is 200-250 mg KOH/g.

12. The feel paint according to claim 1 or 2, characterized in that: the viscosity of the linear polyester polyol resin is 2500 cps/25-3500 cps/25 ℃.

13. The feel paint according to claim 1 or 2, characterized in that: the acid value of the linear polyester polyol resin is 1-4 mg KOH/g.

14. The feel paint according to claim 1 or 2, characterized in that: the hydroxyl value of the linear polyester polyol resin is 100-130 mg KOH/g.

15. The feel paint according to claim 1 or 2, characterized in that: the elastic hand feeling agent is a modified organic silicon high molecular polymer.

16. The feel paint according to claim 1 or 2, characterized in that: the anti-fouling additive is organic silicon modified polyacrylate with hydroxyl.

17. A process for the preparation of a feel paint according to any one of claims 1 to 6, characterized in that: the method comprises the following steps: and mixing the component A and the component B, and adjusting the viscosity.

18. A paint coating with hand feeling is characterized in that: prepared from a feel paint according to any one of claims 1 to 16.

19. Use of a feel paint as claimed in any one of claims 1 to 16 in the manufacture of a protective shell.