TW202227462A - Slurry composition and preparation method thereof - Google Patents

Abstract

The invention provides a slurry composition and a preparation method thereof. The slurry composition includes a filler, a slurry carrier and a dispersant. The slurry carrier includes a solvent or a resin. The dispersant is a small molecule multifunctional crosslinking dispersant, which has at least two crosslinkable double bond functional groups, has a higher boiling point, is thermally stable and has a low polarity, and has good dispersion characteristics for fillers.

Description

Slurry composition and preparation method thereof

The present invention relates to a composition and a preparation method thereof, and in particular to a slurry composition and a preparation method thereof.

At present, the industrial technology of PCB, whether soft board or hard board, is developing towards high frequency, high speed and high density packaging. Corresponding to the development trend of light, thin, portable and multi-functional products, the wiring of copper clad laminates is becoming more and more High density and thinning between layers have put forward more stringent requirements on the impedance characteristics and reliability of transmission lines, as well as the assembly and processing accuracy of components. Under the requirements of high frequency, high speed and miniaturization, high frequency transmission and low loss materials will completely replace transmission lines. The requirements for circuit substrates must meet high heat resistance, low moisture absorption, low dielectric properties and good flame resistance.

With the gradual expansion of the application field of 5G, the demand for high-frequency and high-speed materials has gradually grown, and it has driven the development of various electronic devices to be lighter, thinner and smaller, and PCB boards used to carry electronic components or carriers used to carry semiconductor chips have also been Synchronization requires thinning. At the same time, in response to the heat generation and heat dissipation problems caused by the denser component density, the PCB or carrier board is also required to have higher dimensional stability requirements.

It is known that the most effective way to improve the dimensional stability of copper clad laminates and substrates is to add a higher proportion of fillers in the resin glue. By choosing the type of filler, particle size, and addition ratio, it can simultaneously improve dimensional stability and The effect of improving the heat dissipation capacity. However, a high filler ratio will cause the viscosity of the resin glue to increase significantly, which is not conducive to processing; at the same time, with the increase of the filler ratio, the filler particles will be more and more likely to aggregate and not be uniformly dispersed in the resin glue, resulting in subsequent processing. defects and poor quality. In order to solve the dispersion problem of high filler ratio, it is common to add additional dispersant to the resin glue to help the filler particles disperse well in the resin glue.

In addition, in order to make the resin glue with high filler ratio easy to process and use, another solution is to prepare a high solid content filler slurry (Slurry) in advance, and then add this slurry to the resin glue for mixing. Such filler slurry generally contains a high proportion of filler particles, a medium solvent or resin used as a slurry carrier, and a dispersant. Since a high proportion of filler is required in the slurry, the dispersing effect of the dispersant on the filler and the compatibility with the solvent or resin directly determine the viscosity and uniformity of the slurry during the preparation and stirring process, and the filler particles in the slurry. Whether there is agglomeration and the stability of the slurry itself will affect the final performance of the slurry added to the resin glue.

At the same time, the development trend of the coating and ink industry is gradually moving towards the direction of low VOC and high solid content, the purpose of which is to reduce the harm to the environment during the construction and drying process of the coating. However, various functional coatings or inks often need to add various functional fillers, such as pigments or fillers, according to the application. Examples of pigments such as titanium dioxide, carbon black, aluminum powder, organic pigments or other electroplating toners. Examples of functional fillers include silver powder, nickel powder, magnesium oxide, aluminum oxide, glass frit or aluminum hydroxide. As the proportion of pigments or fillers is gradually increased in the formula, the viscosity of the overall formula will also be greatly increased, and it is easy to cause uneven dispersion and agglomeration between particles, and similar processing and quality problems as mentioned above occur.

In view of the above problems, most of the conventional technologies use the technical means of adding dispersants. On the one hand, the added amount is not too large to affect the physical properties too much, and on the other hand, it is easy to obtain and does not lead to a significant increase in cost. However, the conventional dispersants are mostly non-reactive dispersants, which are prone to several problems in terms of product reliability. In general, common dispersants such as modified polysiloxane (modified silicone oil) are characterized by low surface energy, good encapsulation of filler particles and compatibility with resin systems, but due to the dispersant itself It does not participate in the curing reaction of the resin. Therefore, it can be regarded as the presence of plasticizers in the cured material, which will negatively affect the physical properties of the material, such as lowering the Tg point of the material, reducing mechanical properties or reducing weather resistance.

Based on the above, a small-molecule multifunctional cross-linking dispersant was developed, which has a high boiling point and good dispersing effect, can participate in the cross-linking reaction of the resin system, is thermally stable and has low polarity, and can prevent subsequent precipitation problems. A goal that those skilled in the art are eager to develop.

The invention provides a slurry composition and a preparation method thereof. The slurry composition contains a dispersant, wherein the dispersant has at least two functional groups that can cross-link double bonds, has a high boiling point, is thermally stable and polar It can be used with epoxy resin, polyurethane acrylic resin, polyphenylene ether, polytetrafluoroethylene, hydrocarbon resin and other resins to prepare a stable slurry.

式（1） 在式（1）中，X為直鏈或支鏈的C1至C6烷基、環烷基或磺醯基，R1為直鏈或支鏈的C1至C6烷基或芳基，R2為C1至C6的烷基，R3為帶有可交聯雙鍵的官能基，n+m為1至8的正整數，

式（2） 在式（2）中，X為直鏈或支鏈的C1至C6烷基、環烷基或磺醯基，R1為直鏈或支鏈的C1至C6烷基或芳基，R3為帶有可交聯雙鍵的官能基，a為1至4的正整數。 The slurry composition of the present invention includes a filler, a slurry carrier and a dispersant. Slurry carriers include solvents or resins. The structure of the dispersant is represented by formula (1) or formula (2):

Formula (1) In formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is an alkyl group of C1 to C6, R3 is a functional group with a crosslinkable double bond, n+m is a positive integer from 1 to 8,

Formula (2) In formula (2), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R3 is a functional group with a crosslinkable double bond, and a is a positive integer of 1 to 4.

In an embodiment of the present invention, the functional group with a crosslinkable double bond includes allyl, vinyl, acrylate or methacrylate.

In an embodiment of the present invention, n+m is 2 or 3.

In one embodiment of the present invention, the filler includes silica or alumina.

In an embodiment of the present invention, the solvent includes acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, toluene, propylene glycol methyl ether, isopropanol or petroleum solvent.

In an embodiment of the present invention, the resin includes epoxy resin, polyurethane acrylic resin, polyphenylene ether, polytetrafluoroethylene or hydrocarbon resin.

In an embodiment of the present invention, the content of filler is 30 phr to 70 phr, the content of solvent is 20 phr to 70 phr, and the content of dispersant is 0.5 phr to 5.0 phr.

In an embodiment of the present invention, the content of filler is 30 phr to 50 phr, the content of resin is 40 phr to 70 phr, and the content of dispersant is 0.5 phr to 2.5 phr.

式（1） 在式（1）中，X為直鏈或支鏈的C1至C6烷基、環烷基或磺醯基，R1為直鏈或支鏈的C1至C6烷基或芳基，R2為C1至C6的烷基，R3為帶有可交聯雙鍵的官能基，n+m為1至8的正整數，

式（2） 在式（2）中，X為直鏈或支鏈的C1至C6烷基、環烷基或磺醯基，R1為直鏈或支鏈的C1至C6烷基或芳基，R3為帶有可交聯雙鍵的官能基，a為1至4的正整數。 The preparation method of the slurry composition of the present invention, for preparing the above-mentioned slurry composition, includes the following steps. The filler, slurry carrier and dispersant are mixed, and the slurry carrier includes a solvent or resin. After that, stirring is performed to break the agglomeration of filler particles in the filler, so that the filler particles are uniformly dispersed in the slurry carrier to form a slurry composition. The structure of the dispersant is represented by formula (1) or formula (2):

Formula (1) In formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is an alkyl group of C1 to C6, R3 is a functional group with a crosslinkable double bond, n+m is a positive integer from 1 to 8,

Formula (2) In formula (2), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R3 is a functional group with a crosslinkable double bond, and a is a positive integer of 1 to 4.

In an embodiment of the present invention, the functional group with a crosslinkable double bond includes allyl, vinyl, acrylate or methacrylate.

In an embodiment of the present invention, n+m is 2 or 3.

In one embodiment of the present invention, the filler includes silica or alumina.

In an embodiment of the present invention, the solvent includes acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, toluene, propylene glycol methyl ether, isopropanol or petroleum solvent.

In an embodiment of the present invention, the resin includes epoxy resin, polyurethane acrylic resin, polyphenylene ether, polytetrafluoroethylene or hydrocarbon resin.

In an embodiment of the present invention, the stirring method includes ball milling, double-shaft stirring or three-drum grinding.

Based on the above, the present invention provides a slurry composition and a preparation method thereof. The slurry composition contains a dispersant, wherein the dispersant has at least two functional groups capable of crosslinking double bonds, has a high boiling point, and is resistant to heat. Stable and low polarity, with good dispersion properties for fillers, it can be used with resins to produce a stable slurry. In more detail, the dispersant of the present invention has reduced its own polarity due to silane modification, and has at least two double bond functional groups that can participate in the cross-linking reaction, so it is especially suitable for high-frequency and high-speed copper clad laminates. in the resin system. In addition, the dispersant of the present invention is also suitable for use in paint or ink systems, especially photo-curable paint or ink systems. The dispersant and the photo-curable resin are cross-linked by the action of the photoinitiator to prevent subsequent possible occurrence of Precipitation and reliability issues.

Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are exemplary, and the present disclosure is not limited thereto.

As used herein, a range represented by "one value to another value" is a general representation that avoids listing all the values in the range in the specification. Accordingly, the recitation of a particular numerical range includes any numerical value within that numerical range as well as a smaller numerical range bounded by any numerical value within that numerical range, as if the arbitrary numerical value and the smaller numerical range were written in the description in the specification The value range is the same.

The present invention provides a slurry composition comprising a filler, a slurry carrier and a dispersant. In more detail, the filler may include silica or alumina. Slurry carrier can include solvent or resin, wherein solvent can include acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, toluene, propylene glycol methyl ether, isopropanol or petroleum solvent, resin can include epoxy resin, polyurethane acrylic resin, polyphenylene ether, teflon or hydrocarbon resin. However, the present invention is not limited thereto. In the slurry composition of the present invention, the content of the filler is, for example, 30 phr to 70 phr, the content of the solvent is, for example, 20 phr to 70 phr, and the content of the dispersant is, for example, 0.5 phr to 5.0 phr, or the content of the filler is, for example, 30 phr to 50 phr, the resin content is, for example, 40 phr to 70 phr, and the dispersant content is, for example, 0.5 phr to 2.5 phr.

式（1） 在式（1）中，X為直鏈或支鏈的C1至C6烷基、環烷基或磺醯基，R1為直鏈或支鏈的C1至C6烷基或芳基，R2為C1至C6的烷基，R3為帶有可交聯雙鍵的官能基，n+m為1至8的正整數，n+m較佳為2或3，

式（2） 在式（2）中，X為直鏈或支鏈的C1至C6烷基、環烷基或磺醯基，R1為直鏈或支鏈的C1至C6烷基或芳基，R3為帶有可交聯雙鍵的官能基，a為1至4的正整數。 圖1為本發明分散劑的IR光譜圖，其中1600 cm-1處為雙鍵的表徵訊號。 In this embodiment, the structure of the dispersant can be represented by formula (1) or formula (2):

Formula (1) In formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is a C1-C6 alkyl group, R3 is a functional group with a crosslinkable double bond, n+m is a positive integer from 1 to 8, n+m is preferably 2 or 3,

Formula (2) In formula (2), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R3 is a functional group with a crosslinkable double bond, and a is a positive integer of 1 to 4. Figure 1 is the IR spectrum of the dispersant of the present invention, wherein 1600 cm-1 is the characteristic signal of the double bond.

In more detail, in formula (1) and formula (2), R3 is a functional group with a cross-linkable double bond, and the functional group with a cross-linkable double bond may include acryl (allyl), vinyl group (vinyl), acrylate (acrylate) or methacrylate (methacrylate), but the present invention is not limited to this. In addition, it must be noted that, in the formula (1) and the formula (2), R3 may contain an oxygen atom or may not contain an oxygen atom. If R3 contains an oxygen atom, for example, an oxygen atom can be attached first, and then a functional group with a crosslinkable double bond can be attached.

反應式（1） 在反應式（1）中，X為直鏈或支鏈的C1至C6烷基、環烷基或磺醯基，R1為直鏈或支鏈的C1至C6烷基或芳基，R2為C1至C6的烷基，R3為帶有可交聯雙鍵的官能基，n+m為1至8的正整數，n+m較佳為2或3，a為1至4的正整數。 At the same time, the present invention also proposes a method for preparing a dispersant, which is used to prepare the above-mentioned dispersants represented by formula (1) and formula (2), and its synthesis reaction formula is represented by reaction formula (1):

Reaction formula (1) In reaction formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, and R1 is a linear or branched C1 to C6 alkyl or aryl group group, R2 is a C1-C6 alkyl group, R3 is a functional group with a crosslinkable double bond, n+m is a positive integer from 1 to 8, n+m is preferably 2 or 3, and a is 1 to 4 positive integer of .

In more detail, in the reaction formula (1), R3 is a functional group with a cross-linkable double bond, and the functional group with a cross-linkable double bond may include allyl, vinyl, acrylate or methacrylate, but the present invention is not limited thereto. In addition, it must be noted that, in the reaction formula (1), R3 may contain an oxygen atom or not. If R3 contains an oxygen atom, for example, an oxygen atom can be attached first, and then a functional group with a crosslinkable double bond can be attached.

As shown in the above reaction formula (1), the present invention mainly utilizes the combination of a diallyl bisphenol compound with hydroxyl groups at both ends and a functional group with at least one alkoxy group and at least one cross-linkable double bond at the end group. Silane is subjected to a dealcoholization reaction at a high temperature under the action of a catalyst to obtain a dispersant having a functional group having a crosslinkable double bond at the end group (ie, the dispersant represented by formula (1) and formula (2)).

In this embodiment, the reaction temperature of the reaction formula (1) is, for example, 100°C to 180°C, preferably 130°C to 160°C, and the reaction time is, for example, 2 hours to 15 hours. In more detail, the diallyl bisphenol compound and the silane having a functional group having a crosslinkable double bond can be placed at the bottom of the reaction tank for reaction, or the diallyl bisphenol compound can be placed at the bottom of the reaction tank. , the silane with the functional group that can cross-link the double bond is fed and reacted by dropwise addition, and the dropwise addition time is, for example, 1 hour to 10 hours. Calculated in terms of the molar ratio of the hydroxyl group of the diallyl bisphenol compound to the alkoxy silane of the dialkoxysilane containing a functional group with a cross-linkable double bond, the diallyl bisphenol compound has a The ratio of the dialkoxysilane of the functional group connecting the double bond is, for example, 1:0.5 to 1:4.0.

In this embodiment, the amount of the catalyst in the reaction formula (1) is, for example, 500 ppm to 5000 ppm relative to the weight of the diallyl bisphenol compound. The types of catalysts can include, but are not limited to, acid catalysts, base catalysts, metal compound catalysts, ester catalysts or combinations thereof, preferably ethyltriphenylphosphine chloride (ETPPCl), ethyltriphenylphosphine bromide ( ETPPBr), ethyltriphenylphosphine iodide (ETPPI), ethyltriphenylphosphine acetate (ETPPAAc), tetrabutylammonium bromide (TBAB), triphenylphosphine (TPP) or tetra-n-butylammonium acetate (TBAAc), but the present invention is not limited to this.

式（A） 如同上文所述，在式（A）中，R1為直鏈或支鏈的C1至C6烷基或芳基，R2為C1至C6的烷基，R3為帶有可交聯雙鍵的官能基，帶有可交聯雙鍵的官能基可包括丙烯基（allyl）、乙烯基（vinyl）、丙烯酸基（acrylate）或甲基丙烯酸基（methacrylate），但本發明並不以此為限。在本實施例中，式（A）的具體例可包括甲基乙烯基二甲氧基矽烷、甲基乙烯基二乙氧基矽烷、烯丙基甲基二甲氧基矽烷、1-烯丙基-2,2-二甲氧基-1,2-氮雜矽環戊烷或其組合，但本發明並不以此為限。具體案例的化學結構式如下所示：

甲基乙烯基二甲氧基矽烷

1-(甲基丙烯醯氧甲基)甲基二甲氧基矽烷

3-(甲基丙烯醯氧丙基)甲基二甲氧基矽烷

1-烯丙基-2,2-二甲氧基-1,2-氮雜矽環戊烷 In the reaction formula (1), the alkoxysilane containing a functional group with a crosslinkable double bond used in the present invention is represented by the formula (A):

Formula (A) As mentioned above, in formula (A), R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is a C1 to C6 alkyl group, and R3 is a cross-linkable alkyl group. The functional group of the double bond, the functional group with the cross-linkable double bond may include allyl, vinyl, acrylate or methacrylate, but the present invention does not This is limited. In this embodiment, specific examples of formula (A) may include methylvinyldimethoxysilane, methylvinyldiethoxysilane, allylmethyldimethoxysilane, 1-allyl group-2,2-dimethoxy-1,2-azasilacyclopentane or a combination thereof, but the present invention is not limited thereto. The chemical structural formula of the specific case is as follows:

Methylvinyldimethoxysilane

1-(Methacrylooxymethyl)methyldimethoxysilane

3-(Methacryloyloxypropyl)methyldimethoxysilane

1-Allyl-2,2-dimethoxy-1,2-azasilacyclopentane

On the other hand, the present invention also provides a preparation method of a slurry composition for preparing the above-mentioned slurry composition, comprising the following steps. The filler, the slurry carrier and the dispersant are mixed, the slurry carrier includes a solvent or a resin, and the structure of the dispersant is represented by formula (1) or formula (2). After that, stirring is performed to break the agglomeration of filler particles in the filler, so that the filler particles are uniformly dispersed in the slurry carrier to form a slurry composition. In more detail, the stirring method may include ball milling, double-shaft stirring or three-drum grinding, but the present invention is not limited thereto. In the present invention, the agglomeration between filler particles is broken by the dispersing effect and stirring of the dispersant on the filler, thereby forming a stable slurry composition. The slurry composition can be further used as a raw material to be mixed with the resin glue and then processed and cured. The pre-dispersion effect of the slurry enables the filler particles to be easily dispersed in the resin glue, which improves the convenience of processing and reduces the problem of filler dispersion after curing. uniform defects. Since the relevant details of the filler, solvent, resin, and structures of formula (1) and formula (2) have been described in detail above, they will not be repeated here.

In this embodiment, the order of mixing and adding the filler, the slurry carrier and the dispersant can be carried out in two different ways. The first way is to pre-dissolve the dispersant in the resin or solvent, and then add the filler. The second method is to premix the solvent or resin with the filler first, and then add the dispersant. After the filler, the slurry carrier and the dispersant are preliminarily mixed, the mixture is sufficiently stirred to obtain the slurry of the present invention. In more detail, the stirring method may include ball milling, double-shaft stirring or three-drum grinding, but the present invention is not limited thereto.

Hereinafter, the slurry composition proposed by the present invention and its preparation method will be described in detail by means of experimental examples. However, the following experimental examples are not intended to limit the present invention. Experimental example

In order to prove that the slurry composition and the preparation method of the present invention effectively exert the effect of dispersing and anti-sedimentation, the following experimental example is specially made. Example 1

The multifunctional dispersant of the present invention and cyclohexanone are uniformly mixed at a weight ratio of 5phr: 25phr, and then 70phr of spherical silica filler without surface treatment is added. With simple stirring, the filler is initially mixed with the cyclohexanone solution containing the dispersant of the present invention. After the mixture was sealed, it was mixed with a twin-shaft mixer (planetary mixer) with high shear force. The stirring conditions were 2000 rpm for 10 min, followed by 2200 rpm for 2 min. After stirring, it was cooled and allowed to stand. The appearance of the sample was visually observed, and after standing for one day, the sample was inverted to observe the sedimentation state at the bottom of the sample. Comparative Example 1

Prepared and measured according to the procedure of Example 1, but changed the weight ratio of dispersant:cyclohexanone to 0:30 phr.

The formulation content and observation results of Example 1 and Comparative Example 1 are shown in Table 1 below. As shown in Table 1, in the slurry (Slurry) prepared by adding the dispersant of the present invention in Example 1, the weight ratio of the filler can be as high as 70wt%, and there is no obvious precipitation at the bottom of the slurry after standing for one day; In Comparative Example 1 to which the dispersant of the present invention was added, most of the fillers settled at the bottom after standing for one day. It can be seen that Example 1 shows that the dispersant of the present invention effectively exerts the effect of dispersing and anti-settling in this slurry system. Table 1 filler solvent additive Slurry appearance Slurry stability Spherical SiO2 without surface treatment Cyclohexanone Dispersant of the present invention Manual shaking After standing for one day, observe the phenomenon of filler precipitation Example 1 70 25 5 Free-flowing dispersion No or little precipitation Comparative Example 1 70 30 0 Free-flowing dispersion most of the precipitation Example 2

The dispersant of the present invention and cyclohexanone are mixed uniformly at a weight ratio of 1.4phr: 28.6phr, and then 70phr of surface-treated crushed silica filler (manufacturer: Sibelco, model: FS04ARV) is added. With simple stirring, the filler is initially mixed with the cyclohexanone solution containing the dispersant of the present invention. After the mixture was sealed, it was mixed with a twin-shaft mixer (planetary mixer) with high shear force. The stirring conditions were 2000 rpm for 10 min, followed by 2200 rpm for 2 min. After stirring, it was cooled and allowed to stand. The appearance of the sample was visually observed, and after standing for one day, the sample was inverted to observe the sedimentation state at the bottom of the sample. .Example 2-1

Prepare and measure according to the procedure of Example 2, but change the order of mixing and adding filler, slurry carrier and dispersant, premix cyclohexanone and surface-treated crushed silica filler first, and then add dispersant. Comparative Example 2

Prepared and measured according to the procedure of Example 2, but changed the weight ratio of dispersant:cyclohexanone to 0:30 phr.

The formulation contents and observation results of Example 2, Example 2-1 and Comparative Example 2 are shown in Table 2 below. As shown in Table 2, in the slurry (Slurry) prepared by adding the dispersant of the present invention in Example 2, the weight ratio of the filler can be as high as 70 wt%, and there is no obvious precipitation at the bottom of the slurry after standing for one day; and Comparative Example 2 without the addition of the dispersant of the present invention showed a non-flowing paste after the completion of the biaxial stirring, and there were still undispersed filler agglomerates at the bottom of the sample. Example 2 shows that the dispersant of the present invention effectively exerts the effect of dispersing and anti-settling in this slurry system. In addition, the flow situation of Example 2-1 was slower than that of Example 2 after cooling to room temperature, but the flow situation after being placed for one day was the same as Example 2. Therefore, it can be known that if the order of mixing and adding of filler, slurry carrier and dispersant is changed, the There are dispersing and anti-settling effects, but it takes a long time to work. Table 2 filler solvent additive Slurry appearance Slurry stability FS04ARV Cyclohexanone Dispersant of the present invention Visually; Shaking Manually After standing for one day, observe the phenomenon of filler precipitation Example 2 70 28.6 1.4 Milky white dispersion, easy to flow No precipitation Example 2-1 70 28.6 1.4 After mixing the samples, the flow situation was slower than that of Example 2 after cooling to room temperature, but the flow situation was the same as Example 2 after standing for one day Comparative Example 2 70 30 0 Viscous paste, no flow, with a large amount of undispersed filler agglomeration at the bottom of the sample Example 3

The dispersant of the present invention and bisphenol A epoxy resin (Nan Ya Plastics, model NPEL128E) were mixed uniformly at a ratio of 1 phr: 49 phr, and then 50 phr of ALM-43 alumina filler (Sumitomo Chemical) was added. Simple stirring is applied to preliminarily mix the filler with the epoxy resin containing the dispersant of the present invention. After the mixture was sealed, it was mixed with a twin-shaft mixer (planetary mixer) with high shear force. The stirring conditions were 2000 rpm for 10 min, followed by 2200 rpm for 2 min. After stirring, it was cooled and allowed to stand. The appearance of the sample was visually observed, and the viscosity of the sample was measured at a constant temperature of 25°C. Dump the sample canister and observe the flow of the sample. Example 3-1

Prepare and measure according to the procedure of Example 3, but change the order of mixing and adding filler, slurry carrier and dispersant, premix bisphenol A epoxy resin and ALM-43 alumina filler first, and then add dispersant. Comparative Example 3

Prepared and measured according to the procedure of Example 3, but changed the weight ratio of dispersant:epoxy resin to 0:50 phr.

The formulation contents and observation results of Example 3, Example 3-1 and Comparative Example 3 are shown in Table 3 below. As shown in Table 3, the dispersant of the present invention can be well compatible with epoxy resins; in the case of the same filler ratio, the dispersant of the present invention can effectively disperse the untreated alumina filler. , thereby reducing the viscosity of the resin system and facilitating subsequent processing. Example 3 shows that the dispersant of the present invention effectively exerts the effects of dispersing, reducing viscosity and improving flow characteristics in this slurry system. In addition, after the example 3-1 is heated to 40 ° C, the viscosity is almost the same as that of the example 3. Therefore, it can be known that if the order in which the filler, the slurry carrier and the dispersant are mixed and added is changed, there are still effects of dispersion and anti-precipitation, but Warming is required to function. Table 3 filler resin additive Slurry appearance fluidity 25°C viscosity 40°C viscosity 50°C viscosity 60°C viscosity ALM43 128E Dispersant of the present invention Visually; shake manually The sample tank is dumped for 3s cps cps cps cps Example 3 50 49 1 Viscous mixture, flowable Smooth flow, faster speed 33,000 7,250 2,000 800 Example 3-1 50 49 1 50,000 7,000 2,100 900 Comparative Example 3 50 50 0 Viscous mixture, flowable Smooth flow, slightly slower 48,000 11,000 3,300 1,700 Example 4

The dispersant of the present invention and bisphenol A type epoxy resin (Nanya Plastics, model NPEL128E) were mixed uniformly at a ratio of 1 phr:49 phr, and then 50 phr of silica filler (Sibelco, model G2C) was added. Simple stirring is applied to preliminarily mix the filler with the epoxy resin containing the dispersant of the present invention. After the mixture was sealed, it was mixed with a twin-shaft mixer (planetary mixer) with high shear force. The stirring conditions were 2000 rpm for 10 min, followed by 2200 rpm for 2 min. After stirring, it was cooled and allowed to stand. The appearance of the sample was visually observed, and the viscosity of the sample was measured at a constant temperature of 25°C. Dump the sample canister and observe the flow of the sample. Example 4-1

Prepare and measure according to the procedure of Example 4, but change the order of mixing and adding filler, slurry carrier and dispersant, premix bisphenol A epoxy resin and silica filler first, and then add dispersant. Comparative Example 4

Prepared and measured according to the procedure of Example 4, but changed the weight ratio of dispersant: epoxy resin to 0:50 phr.

The formulation contents and observation results of Example 4, Example 4-1 and Comparative Example 4 are shown in Table 4 below. As shown in Table 4, the dispersant of the present invention can be well compatible with epoxy resin; in the case of the same filler ratio, the dispersant of the present invention can effectively disperse the untreated silica filler. It can greatly reduce the viscosity of the resin system and improve its flow characteristics, which is convenient for subsequent processing. Example 4 shows that the dispersant of the present invention effectively exerts the effects of dispersing, reducing viscosity and improving flow characteristics in this slurry system. In addition, after the temperature of Example 4-1, the viscosity is almost the same as that of Example 4. Therefore, it can be known that if the order of mixing and adding of filler, slurry carrier and dispersant is changed, the effect of dispersion and anti-precipitation still exists, but it is only necessary to increase the temperature to exert the effect. effect. Table 4 filler resin additive Slurry appearance fluidity 25°C viscosity 40°C viscosity 50 oC viscosity 60 oC viscosity G2C 128E Dispersant of the present invention Visually; Shaking Manually Dump the sample tank for 5s cps cps cps cps Example 4 50 49 1 Viscous mixture, flowable slow flow, fast 92,000 13,000 5,500 1,900 Example 4-1 50 49 1 134,000 12,800 5,400 2,000 Comparative Example 4 50 50 0 Viscous mixture, flowable slow flow, fast 162,000 28,000 13,250 7,000 Example 5

The dispersant of the present invention was mixed well with a polyurethane acrylic resin (Double Bond Chemicals, model Doublemer 553) at a ratio of 1 phr:49 phr, followed by the addition of 50 phr of silica filler (Sibelco, model G2C). Simple stirring is applied to preliminarily mix the filler with the polyurethane acrylic resin containing the dispersant of the present invention. After sealing the mixture, high shear mixing was applied with a twin shaft mixer (planetary mixer) at 2000 rpm for 10 min followed by 2200 rpm for 2 min. Cool and let stand after stirring. The appearance of the sample was visually observed, and the viscosity of the sample was measured at a constant temperature of 25°C. Dump the sample canister and observe the flow of the sample. Comparative Example 5

Prepared and measured according to the procedure of Example 5, but changed the weight ratio of dispersant:polyurethane acrylic resin to 0:50 phr.

The formulation content and observation results of Example 5 and Comparative Example 5 are shown in Table 5 below. As shown in Table 5, the dispersant of the present invention can be well compatible with the polyurethane acrylic resin, and in the case of the same filler ratio, the dispersant of the present invention can effectively play a role in the untreated silica filler Dispersion effect, thereby greatly reducing the viscosity of the resin system and improving its flow characteristics, which is convenient for subsequent processing. Because the dispersant of the present invention has at least two reactive vinyl functional groups, it can participate in the cross-linking reaction of the polyurethane acrylic resin, so it is particularly suitable for use in UV coating systems. Table 5 Numbering filler resin additive Slurry appearance 40°C viscosity 50°C viscosity 60°C viscosity G2C 553 Dispersant of the present invention Visually; shake manually cps cps cps Example 5 50 49 1 Evenly viscous paste 1,090,000 600,000 165,000 Comparative Example 5 50 50 0 Evenly viscous paste 1,400,000 980,000 860,000

In summary, the present invention provides a slurry composition and a preparation method thereof. The slurry composition contains a dispersant, wherein the dispersant has at least two functional groups that can cross-link double bonds and has a relatively high boiling point. It is thermally stable and low in polarity, and has good dispersion properties for fillers, and can be used with resins to prepare a stable slurry. In more detail, the present invention uses the dispersing effect of the dispersant on the filler to break the agglomeration between the filler particles, and the slurry composition can be further used as a raw material to be mixed with the resin glue for further processing and curing.

The dispersant of the present invention has multiple double bonds that can participate in the cross-linking reaction, can be co-cross-linked with other resins containing double bonds, has good dispersing properties for inorganic fillers such as silica and alumina, and can effectively improve the performance of fillers in The addition ratio in the resin glue can improve the dimensional stability. In addition, the molecular structure of the dispersant of the present invention is symmetrical and low in polarity, and has good electrical properties, which is especially suitable for the requirements of high-frequency and high-speed materials. The molecular structure has a core of bisphenol A and stable Si-O chemical bonds, and has certain It has excellent flame retardant properties, and a single molecule has four cross-linkable double bonds and two silicon atoms, which has excellent affinity and dispersibility for fillers. In this way, the dispersant of the present invention can participate in the curing and cross-linking reaction of the resin system, so that its addition amount has greater elasticity, and at the same time solves the problems of conventional non-reactive dispersants, and the dispersant of the present invention Most organic solvents are compatible and can be used in both solvent and solvent-free systems.

none

Fig. 1 is the IR spectrum of the dispersant of the present invention.

Claims (15)

A slurry composition comprising: a filler; a slurry carrier including a solvent or a resin; and a dispersant, wherein the structure of the dispersant is represented by formula (1) or formula (2):

Formula (1) In formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is an alkyl group of C1 to C6, R3 is a functional group with a crosslinkable double bond, n+m is a positive integer from 1 to 8,

Formula (2) In formula (2), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R3 is a functional group with a crosslinkable double bond, and a is a positive integer of 1 to 4. The slurry composition according to claim 1, wherein the functional group with a crosslinkable double bond comprises allyl, vinyl, acrylate or methacrylate ). The slurry composition according to claim 1, wherein n+m is 2 or 3. The slurry composition of claim 1, wherein the filler comprises silica or alumina. The slurry composition according to claim 1, wherein the solvent comprises acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, toluene, propylene glycol methyl ether, isopropanol or petroleum solvent. The slurry composition according to claim 1, wherein the resin comprises epoxy resin, polyurethane acrylic resin, polyphenylene ether, polytetrafluoroethylene or hydrocarbon resin. The slurry composition according to claim 1, wherein the content of the filler is 30 phr to 70 phr, the content of the solvent is 20 phr to 70 phr, and the content of the dispersant is 0.5 phr to 5.0 phr. The slurry composition according to claim 1, wherein the content of the filler is 30 phr to 50 phr, the content of the resin is 40 phr to 70 phr, and the content of the dispersant is 0.5 phr to 2.5 phr. A preparation method of a slurry composition for preparing the slurry composition according to any one of claim 1 to claim 8, comprising: mixing a filler, a slurry carrier and a dispersant, the slurry carrier including a solvent or resin; and stirring to break the agglomeration of filler particles in the filler, so that the filler particles are uniformly dispersed in the slurry carrier to form a slurry composition, wherein the structure of the dispersant It is represented by formula (1) or formula (2):

Formula (1) In formula (1), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R2 is an alkyl group of C1 to C6, R3 is a functional group with a crosslinkable double bond, n+m is a positive integer from 1 to 8,

Formula (2) In formula (2), X is a linear or branched C1 to C6 alkyl, cycloalkyl or sulfonyl group, R1 is a linear or branched C1 to C6 alkyl or aryl group, R3 is a functional group with a crosslinkable double bond, and a is a positive integer of 1 to 4. The method for preparing a slurry composition according to claim 9, wherein the functional group with a crosslinkable double bond comprises allyl, vinyl, acrylate or methacrylic acid base (methacrylate). The preparation method of the slurry composition according to claim 9, wherein n+m is 2 or 3. The preparation method of the slurry composition according to claim 9, wherein the filler comprises silica or alumina. The preparation method of the slurry composition according to claim 9, wherein the solvent comprises acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, toluene, propylene glycol methyl ether, isopropanol or petroleum solvent. The preparation method of the slurry composition according to claim 9, wherein the resin comprises epoxy resin, polyurethane acrylic resin, polyphenylene ether, polytetrafluoroethylene or hydrocarbon resin. The method for preparing a slurry composition according to claim 9, wherein the stirring method includes ball milling, biaxial stirring or three-roll milling.

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