Phenolic resin composite material and use thereof

Abstract

To provide a phenol resin composite material having both excellent processability and mechanical strength.SOLUTION: To provide a phenolic resin composite material. The present phenolic resin composite material comprises (A) a phenolic resin and (B) a glass fiber, wherein the ratio (L / D) of the length L to the diameter D of the glass fiber (B) satisfies the following condition: based on the total number of the glass fibers, 1.7% to 22.4% of the glass fibers have an L / D value of 5 to 10, 77% to 98.3% of the glass fibers have an L / D value of greater than 10 and less than or equal to 100, and less than 1.4% of the glass fibers have an L / D value of greater than 100. The unit of the length L and the diameter D is μm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Priority claims This application claims the benefit of Taiwan Patent Application No. 113123844, filed June 26, 2024, the subject matter of which is incorporated herein by reference in its entirety.

[0002] The present invention provides a phenolic resin composite material, in particular a phenolic resin composite material with excellent processability and mechanical strength. [Background technology]

[0003] Phenolic resin is a resin material commonly used in the Bakelite process. Glass fiber-reinforced phenolic resin composites are widely used in various electrical materials due to their lightweight and high strength. In recent years, due to the need for energy conservation, these composites have increasingly been applied to electrical machinery and automotive interior components. As the required strength increases, the proportion of glass fiber used in phenolic resin composites has gradually increased, and the requirements for uniformity of the glass fiber length distribution have also increased.

[0004] However, using a high proportion of glass fibers can reduce the processability of phenolic resin composites. In particular, using long glass fibers can cause problems such as fuzzing, and excessive fiber length can significantly reduce the apparent specific gravity of the phenolic resin composite, making continuous production difficult due to bridging during injection molding. On the other hand, using short glass fibers can improve the processability of phenolic resin composites or increase the apparent specific gravity, but can also result in insufficient strength. Summary of the Invention [Problem to be solved by the invention]

[0005] In view of the above technical problems, the present invention aims to provide a phenolic resin composite material that combines excellent processability and mechanical strength. This is achieved by using glass fibers with a specific length-to-diameter ratio, which can provide the phenolic resin composite material with excellent processability and mechanical strength. In particular, when the phenolic resin composite material further contains a silane coupling agent (preferably a ureidosilane coupling agent), its mechanical strength can be further increased. [Means for solving the problem]

[0006] Therefore, an object of the present invention is to provide a phenolic resin composite material comprising (A) a phenolic resin and (B) glass fibers, wherein the ratio (L / D) of the length L of the glass fibers (B) to the diameter D thereof satisfies the following conditions: based on the total number of the glass fibers, 1.7% to 22.4% of the glass fibers have an L / D value of 5 to 10, 77% to 98.3% of the glass fibers have an L / D value greater than 10 and equal to or less than 100, and less than 1.4% of the glass fibers have an L / D value greater than 100; and the length L and the diameter D are expressed in μm.

[0007] In one embodiment of the present invention, based on the total number of the glass fibers, 40% to 85% of the glass fibers have an L / D value of more than 10 and 30 or less.

[0008] In one embodiment of the present invention, the diameter D of the glass fibers (B) ranges from 6 μm to 14 μm.

[0009] In one embodiment of the present invention, the length L of the glass fiber (B) ranges from 30 μm to 1700 μm.

[0010] In one embodiment of the present invention, the glass fibers (B) have an average length of 100 μm to 400 μm.

[0011] In one embodiment of the present invention, the amount of the glass fiber (B) ranges from 30 parts by weight to 56 parts by weight, based on 100 parts by weight of the phenolic resin composite material.

[0012] In one embodiment of the present invention, the phenolic resin composite further comprises an additive selected from the group consisting of a silane coupling agent, carbon black, a filler, a cure accelerator, a lubricant, a mold release agent, a flame retardant (such as a nitrogen-containing flame retardant compound), and combinations thereof.

[0013] In one embodiment of the present invention, the phenolic resin composite material further includes a silane coupling agent, which may be a ureidosilane coupling agent, and the amount of the silane coupling agent is in the range of 0.2 to 7.0 parts by weight based on 100 parts by weight of the glass fiber (B).

[0014] In one embodiment of the present invention, the phenolic resin composite further comprises carbon black, and the amount of the carbon black ranges from 1.0 parts by weight to 2.0 parts by weight, based on 100 parts by weight of the phenolic resin composite.

[0015] In one embodiment of the present invention, the apparent specific gravity of the phenolic resin composite material is 0.64 g / cm 3 ~0.75g / cm 3 The apparent specific gravity is measured in accordance with JIS K6911.

[0016] Another object of the present invention is to provide a phenolic resin product made from the above-mentioned phenolic resin composite material.

[0017] To make the above objectives, technical features and advantages of the present invention more clear, the present invention will be described in detail below with reference to some specific embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0018] Some specific embodiments of the present invention are described in detail, however, the present invention may be embodied in various embodiments and should not be limited to the embodiments set forth herein.

[0019] Unless otherwise specified, the terms "a", "the", and the like used in this specification and claims are intended to include both the singular and the plural.

[0020] The main advantage of the present invention over the prior art is in particular the controlled proportion of glass fibers with different length L to diameter D ratios (L / D) to provide superior processability and mechanical strength. Details regarding the phenolic resin composite of the present invention are provided below.

[0021] Here, glass fiber refers to a fiber having a ratio (L / D) of length L to diameter D of 5 or more. A glass material with an L / D value of less than 5 can only function as a filler, but cannot provide the effect of improving the processability or mechanical strength of the composite material.

[0022] 1. Phenolic resin composite materials The phenolic resin composite material of the present invention comprises (A) a phenolic resin and (B) glass fibers, and may optionally further comprise optional components. A detailed description of each component is provided below.

[0023] 1.1.(A) Phenolic resin Phenolic resins can be synthesized by polymerization of phenol and aldehyde. Based on the degree of reaction, they can be classified into A-stage phenolic resins, B-stage phenolic resins, and C-stage phenolic resins. A-stage phenolic resins refer to the initial polymerization product, such as novolac resins or resole resins. B-stage phenolic resins and C-stage phenolic resins refer to the products obtained by further reaction or crosslinking under the influence of heat or mechanical force, with C-stage phenolic resins being the most highly crosslinked. In one embodiment of the present invention, the phenolic resin (A) is a B-stage phenolic resin or a C-stage phenolic resin obtained by further reaction or crosslinking of novolac resins and / or resole resins under the influence of heat or mechanical force.

[0024] The preparation method of the novolak resin and the resole resin is not particularly limited and is not the technical focus of the present invention. Those skilled in the art can obtain the resins through commercial purchase or based on the teachings of the specification of this application, and can use their ordinary knowledge to prepare the resins, for example, by condensation polymerization of phenol and formaldehyde.

[0025] In the phenolic resin composite of the present invention, the amount of phenolic resin can range from 25 to 50 parts by weight, based on 100 parts by weight of the phenolic resin composite. For example, based on 100 parts by weight of the phenolic resin composite, the amount of phenolic resin can be 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 parts by weight, or a range between any two of the values ​​recited herein.

[0026] 1.2.(B) Glass fiber The glass fibers (B) can improve the mechanical strength of the phenolic resin composite material. The glass fibers include glass fibers having an L / D value of 5 to 10, glass fibers having an L / D value of more than 10 and not more than 100, and glass fibers having an L / D value higher than 100. Alternatively, the glass fibers (B) consist essentially of glass fibers having an L / D value of 5 to 10, glass fibers having an L / D value of more than 10 and not more than 100, and glass fibers having an L / D value higher than 100. Alternatively, the glass fibers (B) consist essentially of glass fibers having an L / D value of 5 to 10, glass fibers having an L / D value of more than 10 and not more than 100, and glass fibers having an L / D value higher than 100. The length L and diameter D are expressed in μm. The glass fibers (B) are preferably dispersed in the phenolic resin (A).

[0027] In the present invention, the amount of glass fibers having an L / D value of 5 to 10 is in the range of 1.7% to 22.4% based on the total number of glass fibers. For example, based on the total number of glass fibers, the amount of glass fibers having an L / D value of 5 to 10 can be 1.7%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, or 22.4%, or a range between any two of the values ​​described herein. Based on the total number of glass fibers, the amount of glass fibers having an L / D value greater than 10 and less than or equal to 100 ranges from 77% to 98.3%. For example, based on the total number of glass fibers, the amount of glass fibers having an L / D value greater than 10 and less than or equal to 100 is 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80%, 80.5%, 81%, 81.5%, 82%, 82.5%, 83%, 83.5%, 84%, 84.5%, 85%, 85.5%, 86%, 86.5%, 87%, 87.5%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110.5%, 111%, 112%, 113%, 114%, 115%, 116%, 117%, 118%, 119%, 120%, 121%, 122%, 123%, 124%, 125%, 126%, 127%, 128%, 129%, 130%, 131%, 132%, 133%, 134%, 135%, 136%, 137%, 138%, 139%, 139.5%, 139%, 140%, 141%, 142%, 143%, 144%, 145%, 146%, 147%, 148%, 149%, The L / D value may be 0.5%, 88%, 88.5%, 89%, 89.5%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, or 98.3%, or within a range between any two of the values ​​described herein. Based on the total number of glass fibers, the amount of glass fibers having an L / D value greater than 100 is less than 1.4%. For example, based on the total number of glass fibers, the amount of glass fibers having an L / D value higher than 100 can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, or 1.3%, or within a range between any two of the values ​​described herein. When the ratio (L / D) of the length L to the diameter D of the glass fiber (B) satisfies the above-mentioned conditions, the phenolic resin composite can have excellent apparent specific gravity, good injection molding processability, and excellent impact strength, flexural strength, and flexural modulus.

[0028] In a preferred embodiment of the present invention, the amount of glass fibers having an L / D value of more than 10 and not more than 30, based on the total number of glass fibers, ranges from 40% to 85%. For example, the amount of glass fibers having an L / D value of more than 10 and not more than 30, based on the total number of glass fibers, can be 40%, 41%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 84%, or 85%, or a range between any two of the values ​​described herein. When the above-mentioned conditions are met, the phenolic resin composite material of the present invention can have better mechanical strength and processability.

[0029] In a preferred embodiment of the present invention, the amount of glass fibers having an L / D value higher than 170 is less than 0.5%, for example, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or 0%, or within a range between any two of the values ​​described herein, more preferably 0%, based on the total number of glass fibers. Under such conditions, the phenolic resin composite material of the present invention can have better mechanical strength and processability.

[0030] In the present invention, the L / D value of the glass fiber (B) can be observed and calculated with the aid of a scanning electron microscope (SEM). Specifically, a material image can be taken at 100x magnification using a scanning electron microscope, and the length L of all fillers in the image can be calculated using software. Based on the known diameter D, the L / D values ​​of all fibers can be calculated and statistically analyzed. Here, the calculated image area includes more than 1,000 fibers.

[0031] In one embodiment of the present invention, the diameter D of the glass fiber (B) is in the range of 6 μm to 14 μm, more particularly 7 μm to 13 μm. For example, the diameter D of the glass fiber (B) can be 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm, 10.5 μm, 11 μm, 11.5 μm, 12 μm, 12.5 μm, 13 μm, 13.5 μm, or 14 μm, or within a range between any two of the values ​​described herein. The diameter D of the individual fibers of the glass fiber (B) can be uniform or different, although a uniform diameter is preferred.

[0032] In one embodiment of the present invention, the length L of the glass fiber (B) is in the range of 30 μm to 1700 μm. For example, the length L of the glass fiber (B) is 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950 μm, 1000 μm, 1100 μm, 1200 μm, 1300 μm, 1400 μm, 1500 μm, 1600 μm, 1700 μm, 1800 μm, 1900 μm, 2000 μm, 2500 μm, 3000 μm, 3500 μm, 4000 μm, 4500 μm, 5000 μm, 5500 μm, 6000 μm, 6500 μm, 7000 μm, 7500 μm, 8000 μm, 8500 μm, 9 μm, 600 μm, 650 μm, 700 μm, 750 μm, 800 μm, 850 μm, 900 μm, 950 μm, 1000 μm, 1050 μm, 1100 μm, 1150 μm, 1200 μm, 1250 μm, 1300 μm, 1350 μm, 1400 μm, 1450 μm, 1500 μm, 1550 μm, 1600 μm, 1650 μm or 1700 μm, or within a range between any two of the values ​​described herein.

[0033] In one embodiment of the present invention, the average length of the glass fibers (B) is 100 μm to 400 μm, preferably 150 μm to 380 μm, and more preferably 200 μm to 370 μm. For example, the average length of the glass fibers (B) can be 100 μm, 150 μm, 200 μm, 220 μm, 250 μm, 280 μm, 300 μm, 320 μm, 350 μm, 380 μm, or 400 μm, or a range between any two of the values ​​described herein. The average length of "glass fibers (B)" refers to the average length of all more than 1,000 fibers in an image of the material taken at 100x magnification using a scanning electron microscope.

[0034] In the phenolic resin composite of the present invention, the amount of glass fiber (B) can range from 30 to 56 parts by weight, based on 100 parts by weight of the phenolic resin composite. For example, based on 100 parts by weight of the phenolic resin composite, the amount of glass fiber (B) can be 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, or 56 parts by weight, or within a range between any two of the values ​​recited herein.

[0035] 1.3. Optional Additives In addition to the above-mentioned components, the phenolic resin composite may further contain optional additives to adaptively improve the physicochemical properties of the phenolic resin composite. Examples of additives include, but are not limited to, silane coupling agents, carbon black, fillers, curing accelerators, lubricants, mold release agents, and flame retardants. The above-mentioned additives may be used alone or in any combination.

[0036] 1.3.1. Silane coupling agents The phenolic resin composite material may further contain a silane coupling agent. Research has shown that the silane coupling agent can enhance the compatibility between the phenolic resin and the glass fiber, thereby further improving the mechanical strength of the phenolic resin composite material of the present invention. Examples of silane coupling agents include, but are not limited to, ureidosilane coupling agents, epoxysilane coupling agents, aminosilane coupling agents, hydroxylsilane coupling agents, and hydrocarbylsilane coupling agents. The above-mentioned silane agents may be used alone or in any combination. Considering the effect of increasing mechanical strength, it is preferable to use a ureidosilane coupling agent.

[0037] Based on 100 parts by weight of glass fiber (B), the amount of silane agent can range from 0.2 to 7.0 parts by weight. For example, based on 100 parts by weight of glass fibers (B), the amount of silane agent can be 0.2 parts by weight, 0.22 parts by weight, 0.25 parts by weight, 0.5 parts by weight, 0.75 parts by weight, 1 part by weight, 1.25 parts by weight, 1.5 parts by weight, 1.75 parts by weight, 2 parts by weight, 2.25 parts by weight, 2.5 parts by weight, 2.75 parts by weight, 3 parts by weight, 3.25 parts by weight, 3.5 parts by weight, 3.75 parts by weight, 4 parts by weight, 4.25 parts by weight, 4.5 parts by weight, 4.75 parts by weight, 5 parts by weight, 5.25 parts by weight, 5.5 parts by weight, 5.75 parts by weight, 6 parts by weight, 6.25 parts by weight, 6.5 parts by weight, 6.67 parts by weight, or 7.0 parts by weight, or within a range between any two of the values ​​recited herein.

[0038] Carbon black The phenolic resin composite of the present invention can further include carbon black as a colorant to give the material a black color. Based on 100 parts by weight of the phenolic resin composite, the amount of carbon black can range from 1.0 to 2.0 parts by weight. For example, based on 100 parts by weight of the phenolic resin composite, the amount of carbon black can be 1.0, 1.5, or 2 parts by weight, or within a range between any two of the values ​​described herein.

[0039] Fillers The phenolic resin composite material of the present invention may further contain a filler to adaptively improve thermal conductivity and dimensional stability. The filler does not include glass fiber. Examples of fillers include, but are not limited to, clay fillers, alumina fillers, aluminum hydroxide fillers, magnesium hydroxide fillers, silica fillers, talc fillers, magnesium oxide fillers, calcium silicate fillers, zinc borate fillers, kaolin fillers, halloysite fillers, calcium carbonate fillers, mica fillers, and glass fillers. Glass fillers refer to fine materials with a low aspect ratio, such as glass rods with an aspect ratio of less than 5. The addition of glass fillers has the same effect as silica or alumina fillers. They are used to improve the dimensional stability and flame retardancy of the composite material, but do not significantly improve the mechanical strength. Considering the properties required for the composite material, such as mechanical performance, electrical performance, flame retardancy, dimensional stability, and water resistance, it is preferable to use clay, alumina, aluminum hydroxide, magnesium hydroxide, silica, talc, magnesium oxide, calcium silicate, zinc borate, kaolin, or halloysite. The above-mentioned fillers can be used alone or in any combination.

[0040] The shape of the filler is not particularly limited and may be spherical, flake-like, rod-like, irregular, or the like, but the present invention is not limited thereto. Furthermore, based on 100 parts by weight of the phenolic resin composite, the amount of filler may range from 0 to 30 parts by weight. For example, based on 100 parts by weight of the phenolic resin composite, the amount of filler may be 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, or 30 parts by weight, or within a range between any two of the values ​​described herein.

[0041] 1.3.4. Curing accelerator The phenolic resin composite material of the present invention may further contain a curing accelerator to accelerate the curing reaction. The type of curing accelerator is not particularly limited, and any curing accelerator known in the art may be used. Examples of curing accelerators include, but are not limited to, alkaline earth metal oxides or hydroxides such as magnesium oxide, calcium hydroxide, and barium hydroxide, and aromatic carboxylic acids such as salicylic acid and benzoic acid. The above-mentioned curing accelerators may be used alone or in any combination.

[0042] Based on 100 parts by weight of the phenolic resin composite, the amount of cure accelerator can range from 1 part by weight to 20 parts by weight, preferably 1 part by weight to 5 parts by weight. For example, based on 100 parts by weight of the phenolic resin composite, the amount of cure accelerator can be 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, or 20 parts by weight, or a range between any two of the values ​​described herein.

[0043] 1.3.5. Lubricants and release agents The phenolic resin composite of the present invention can further contain a lubricant and / or a mold release agent to reduce friction and adhesion between the composite and the mold, thereby improving processability and facilitating the release of the phenolic resin composite from the mold. Examples of lubricants and mold release agents include, but are not limited to, stearates such as magnesium stearate, calcium stearate, and aluminum stearate; silicone oil; and fluorochemicals. The above-mentioned lubricants and mold release agents can be used alone or in any combination.

[0044] Based on 100 parts by weight of the phenolic resin composite, the amount of lubricant and release agent can each independently range from 0.1 to 3 parts by weight. For example, based on 100 parts by weight of the phenolic resin composite, the amount of lubricant and release agent can each independently be 0.1, 0.5, 1, 1.5, 2, 2.5, or 3 parts by weight, or a range between any two of the values ​​recited herein.

[0045] 1.4. Properties of Phenolic Resin Composites The present invention provides excellent processability and mechanical strength to a phenolic resin composite material by adjusting the L / D ratio distribution of glass fibers in the composite material. The processability can be determined from the apparent specific gravity of the phenolic resin composite material. Typically, a phenolic resin composite with an apparent specific gravity of 0.6 g / cm 3 If the value is equal to or greater than this, it indicates that the processability is good.

[0046] In one embodiment of the present invention, the apparent specific gravity of the phenolic resin composite material is 0.64 g / cm 3 to 0.75 g / cm 3 For example, the apparent specific gravity of a phenolic resin composite is 0.64 g / cm 3 , 0.65g / cm 3 , 0.70g / cm 3 or 0.75g / cm 3 , or can be within a range between any two of the values ​​described herein. The apparent specific gravity is measured in accordance with JIS K6911.

[0047] 2. Preparation of Phenolic Resin Composites The method for preparing the phenolic resin composite material of the present invention is not particularly limited. For example, it can be formed by uniformly mixing a phenolic resin with glass fibers that satisfy the desired L / D ratio conditions. Alternatively, the phenolic resin composite material of the present invention can be formed by mixing a phenolic resin with glass fibers that have a high L / D ratio (e.g., higher than 100), applying mechanical force to break the glass fibers, and controlling the strength of the mechanical force to achieve the desired L / D ratio in the phenolic resin composite material. Methods for applying mechanical force include, but are not limited to, using a screw, roller, or co-kneader to generate mechanical force, and controlling the strength of the mechanical force by factors such as the rotation speed and the gap between the rollers. Specific preparation methods will be described in the examples.

[0048] 3. Applications of phenolic resin composite materials The phenolic resin composite material of the present invention can be further applied to known phenolic resin materials through processes such as granulation and injection molding. Therefore, the present invention also provides a phenolic resin product manufactured using the phenolic resin composite material of the present invention. The phenolic resin product can be prepared by a method such as injection molding, in which the mold temperature used for injection molding can be in the range of 170°C to 190°C, the molding pressure can be in the range of 30 MPa to 200 MPa, and the curing time can be between 30 and 90 seconds.

[0049] The phenolic resin product of the present invention can be widely used in various applications, including, but not limited to, automobile parts, aircraft parts, railway vehicle parts, ship parts, office supplies, various machine parts, housings, etc.

[0050] 4. Working Example 4.1. Test Method The present application is further described by the following embodiments, in which the test device and method are as follows:

[0051] [L / D value of glass fiber test] The distribution of the ratio of length L to diameter D (L / D) of glass fibers is tested according to ISO 1172, Method B. In detail, the test is performed as follows:

[0052] The prepared phenolic resin composite was calcined at 600°C for 3 hours to obtain ash. The resulting ash was then soaked in 35% HCl to dissolve the main filler, after which it was filtered and the filter cake was washed with pure water and alcohol. The dissolution, filtration, and washing steps were repeated as necessary. The filter cake was then dried at 105°C until its weight remained constant, yielding a test sample.

[0053] The test sample was surface-treated using an automatic sputtering machine (model number: JEC-3000FC). The test sample was then observed using a scanning electron microscope (model number: JSM-IT200, available from JEOL Ltd.). A randomly selected observation surface of the test sample was used, and images were taken at 100x magnification and 1280 x 1024 pixel resolution. Using the image and measurement software from Fibermetric and ATMT Measurement, the length L of all fibers in the image was calculated, and the L / D ratios were statistically analyzed for ranges of 5 to 10, greater than 10 but less than 100, and greater than 100. The calculated image area contained more than 1000 fibers.

[0054] [Apparent specific gravity measurement] The apparent specific gravity of phenolic resin composite materials is measured in accordance with JIS K6911:1995. The unit of apparent specific gravity is g / cm. 3 is.

[0055] [Impact test] The resulting phenolic resin composite material was injection molded using a 170-ton injection molding machine equipped with a 56 mm screw (available from Hwa Chin Machinery Factory) along with a mold for JIS standard test specimens, with a volume of 130 cm. 3 The injection conditions are as follows: tube temperature 85°C, mold temperature 170°C, molding pressure 100MPa, injection time 6 seconds, and curing time 60 seconds.

[0056] In accordance with JIS K6911, a Charpy impact test is performed on the test piece using an impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd., and the impact strength is recorded. The unit of impact strength is kJ / cm. 2 is.

[0057] [Bending strength test] The resulting phenolic resin composite material was injection molded using a 170-ton injection molding machine equipped with a 56 mm screw (available from Hwa Chin Machinery Factory) along with a mold for JIS standard test specimens, with a volume of 130 cm. 3The injection conditions are as follows: tube temperature 85°C, mold temperature 170°C, molding pressure 100MPa, injection time 6 seconds, and curing time 60 seconds.

[0058] Test specimens are subjected to bending strength tests using a universal testing machine in accordance with JIS K6911. The bending strength is measured in kgf / mm. 2 is.

[0059] [Flexural modulus] The resulting phenolic resin composite material was injection molded using a 170-ton injection molding machine equipped with a 56 mm screw (available from Hwa Chin Machinery Factory) along with a mold for JIS standard test specimens, with a volume of 130 cm. 3 The injection conditions are as follows: tube temperature 85°C, mold temperature 170°C, molding pressure 100MPa, injection time 6 seconds, and curing time 60 seconds.

[0060] The flexural modulus of the test piece is tested using a universal testing machine in accordance with JIS K 6911. The flexural modulus is measured in MPa.

[0061] [Injection molding processability] The resulting phenolic resin composite material was injection molded using a 170-ton injection molding machine equipped with a 56 mm screw (available from Hwa Chin Machinery Factory) along with a mold for JIS standard test specimens, with a volume of 130 cm. 3 The injection conditions are as follows: tube temperature 85°C, mold temperature 170°C, molding pressure 100MPa, injection time 6 seconds, and curing time 60 seconds.

[0062] The evaluation criteria for injection molding processability are as follows: if the material can be injection molded into 10 or more molded articles in succession, i.e., if 10 or more injection molding operations can be performed, it is recorded as "○", indicating good processability; if the material cannot be injection molded into 10 molded articles in succession, it is recorded as "×", indicating poor processability.

[0063] 4.2. Preparation and Characterization of Phenolic Resin Composites 4.2.1. Examples 1 to 5 and Comparative Examples 1 to 8 [Example 1]

[0064] A resin composition was formed by uniformly mixing 40 parts by weight of a resole resin (available from Chang Chun Plastics), 2 parts by weight of calcium hydroxide (Ca(OH)), 1.5 parts by weight of a reinforcing agent (nitrile rubber NP4060 available from Alplus), 22 parts by weight of a filler (a mixture of aluminum hydroxide and clay in a volume ratio of 3:7 available from Taiwan Fortune Material), 1.5 parts by weight of a lubricant and mold release agent (the lubricant was magnesium stearate available from Color-Ray Trading; the mold release agent was KF-412 available from Shin-Etsu Chemical Co., Ltd.), 1.3 parts by weight of carbon black (available from Asahi Carbon Co., Ltd.), 0.7 parts by weight of a nitrogen-containing flame retardant compound (melamine available from Chang Chun Plastics), and 1.0 part by weight of a ureidosilane coupling agent (VPS-2101 available from Taiwan Evonik Co., Ltd.) using a mixer. Furthermore, 30 parts by weight of glass fibers having a diameter of 10 μm and a length of 1.7 mm were prepared.

[0065] The resin composition and glass fibers were fed into a twin-screw extruder. The resin composition was fed from the head of the extruder, and the glass fibers were fed from the side of the extruder. Mixing in the twin-screw extruder was carried out under the following conditions: the temperature at the front of the extruder was 80°C, the temperatures at the middle and rear (mixing zones) were 90°C, and the screw rotation speed was 189 rpm. After mixing, the resulting phenolic resin composite material product was cooled to room temperature and then crushed into particles.

[0066] [Example 2] A phenolic resin composite was prepared by repeating the procedure of Example 1, except that the amounts of each component in the resin composition were adjusted to 37 parts by weight of resol resin, 1.8 parts by weight of calcium hydroxide, 1.5 parts by weight of reinforcing agent, 1.5 parts by weight of lubricant and release agent combined, 1.3 parts by weight of carbon black, 0.7 parts by weight of nitrogen-containing flame retardant compound, and 1.0 part by weight of ureidosilane coupling agent. No filler was used. Additionally, 55.2 parts by weight of glass fiber with a diameter of 10 μm and a length of 1.7 mm was used.

[0067] [Example 3] A phenolic resin composite was prepared by repeating the procedure of Example 1, except that the amounts of each component in the resin composition were adjusted to 37 parts by weight of resol resin, 1.8 parts by weight of calcium hydroxide, 1.5 parts by weight of reinforcing agent, 10.2 parts by weight of filler, 1.5 parts by weight of lubricant and release agent combined, 1.3 parts by weight of carbon black, 0.7 parts by weight of nitrogen-containing flame retardant compound, and 1.0 part by weight of ureidosilane coupling agent. In addition, 45 parts by weight of glass fiber having a diameter of 10 μm and a length of 1.7 mm was used.

[0068] [Example 4] The preparation procedure of Example 3 was repeated to prepare a phenolic resin composite material, except that the screw rotation speed was adjusted to 244 rpm.

[0069] [Example 5] The preparation procedure of Example 3 was repeated to prepare a phenolic resin composite material, except that the screw rotation speed was adjusted to 284 rpm.

[0070] [Comparative Example 1] The preparation procedure of Example 3 was repeated to prepare a phenolic resin composite material, except that the screw rotation speed was adjusted to 393 rpm.

[0071] Comparative Example 2 The preparation procedure of Example 3 was repeated to prepare a phenolic resin composite material, except that the screw rotation speed was adjusted to 138 rpm.

[0072] Comparative Example 3 A phenolic resin composite material was prepared by repeating the preparation procedure of Example 3, except that glass fibers having a diameter of 10 μm and a length of 3 mm were used instead of the glass fibers having a diameter of 10 μm and a length of 1.7 mm, and the screw rotation speed was adjusted to 138 rpm.

[0073] Comparative Example 4 A phenolic resin composite material was prepared by repeating the preparation procedure of Example 3, except that glass fibers having a diameter of 10 μm and a length of 3 mm were used instead of the glass fibers having a diameter of 10 μm and a length of 1.7 mm.

[0074] Comparative Example 5 A phenolic resin composite material was prepared by repeating the preparation procedure of Example 3, except that glass fibers having a diameter of 10 μm and a length of 3 mm were used instead of the glass fibers having a diameter of 10 μm and a length of 1.7 mm, and the screw rotation speed was adjusted to 244 rpm.

[0075] Comparative Example 6 A phenolic resin composite material was prepared by repeating the preparation procedure of Example 3, except that glass fibers having a diameter of 10 μm and a length of 3 mm were used instead of the glass fibers having a diameter of 10 μm and a length of 1.7 mm, and the screw rotation speed was adjusted to 393 rpm.

[0076] Comparative Example 7 A phenolic resin composite was prepared by repeating the procedure of Example 1, except that the amounts of each component in the resin composition were adjusted to 37 parts by weight of resol resin, 1.8 parts by weight of calcium hydroxide, 1.5 parts by weight of reinforcing agent, 30.2 parts by weight of filler, 1.5 parts by weight of lubricant and release agent combined, 1.3 parts by weight of carbon black, 0.7 parts by weight of nitrogen-containing flame retardant compound, and 1.0 part by weight of ureidosilane coupling agent. In addition, 25 parts by weight of glass fiber having a diameter of 10 μm and a length of 1.7 mm was used.

[0077] [Comparative Example 8] A phenolic resin composite was prepared by repeating the procedure of Example 1, except that the amounts of each component in the resin composition were adjusted to 34 parts by weight of resol resin, 1.5 parts by weight of calcium hydroxide, 1.5 parts by weight of lubricant and release agent combined, 1.3 parts by weight of carbon black, 0.7 parts by weight of a nitrogen-containing flame retardant compound, and 1.0 part by weight of a ureidosilane coupling agent. No filler was used. Additionally, 60 parts by weight of glass fibers with a diameter of 10 μm and a length of 1.7 mm were used.

[0078] [Characteristics analysis] The properties of the phenolic resin composite materials of Examples 1 to 5 and Comparative Examples 1 to 8, including the L / D value of the glass fiber, apparent specific gravity, impact strength, flexural strength, flexural modulus, and injection molding processability, were measured according to the test methods described above, and the results were recorded in Table 1.

[0079] [Table 1]

[0080] As shown in Table 1, the phenolic resin composite materials of Examples 1 to 5 of the present invention, which use resol resin and 10 μm diameter glass fibers as raw materials, exhibit excellent apparent specific gravity, good injection molding processability, and excellent impact strength, flexural strength, and flexural modulus. In contrast, the phenolic resin composite materials of Comparative Examples 1 to 8 do not simultaneously possess these excellent properties. Comparison of Examples 3 to 5 with Comparative Examples 1, 4, and 7 shows that under similar raw material conditions, the phenolic resin composite materials of the present invention have excellent impact strength, flexural strength, and flexural modulus. Comparative Examples 2, 3, and 8 demonstrate that when the amount of glass fibers with an L / D value higher than 100 exceeds the range specified in the present invention, the phenolic resin composite materials have poor processability. Comparative Example 8 even fails to produce a molded product with the desired appearance.

[0081] 4.2.2. Examples 6 to 7 and Comparative Example 9 [Example 6] 31 parts by weight of novolac resin (available from Chang Chun Plastics), 0.5 parts by weight of calcium hydroxide (Ca(OH)), 6 parts by weight of hexamethylenetetramine (available from Chang Chun Plastics), 1.0 part by weight of reinforcing agent (nitrile rubber NP4060, available from Alplus), 10 parts by weight of filler (a mixture of aluminum hydroxide and clay in a volume ratio of 3:7, available from Taiwan Fortune Material), 1.5 parts by weight of carbon black, and 0.6 parts by weight of ureidosilane coupling agent (VPS-2101, available from Taiwan Evonik) were uniformly mixed in a mixer for 20 minutes to form a resin composition. Next, 50 parts by weight of glass fiber with a diameter of 10 μm and a length of 1.7 mm was added thereto and mixed for 1 minute to form a premixed material.

[0082] The premixed material was fed into a two-roll mixer equipped with rollers measuring 8 inches in diameter and 24 inches in length. Mixing was carried out under the following conditions: the gap between the two rollers was set to 0.6 mm, the roller temperature was 90°C to 110°C, the roller rotation speed was 22 rpm, and the mixing time was 180 seconds. After mixing, the resulting phenolic resin composite product was cooled to room temperature and then crushed into particles.

[0083] [Example 7] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 6, except that no ureidosilane coupling agent was used.

[0084] Comparative Example 9 A phenolic resin composite material was prepared by repeating the preparation procedure of Example 6, except that glass fibers having a diameter of 10 μm and a length of 3 mm were used instead of the glass fibers having a diameter of 10 μm and a length of 1.7 mm.

[0085] [Characteristics analysis] The properties of the phenolic resin composite materials of Examples 6 to 7 and Comparative Example 9, including the L / D value of the glass fiber, apparent specific gravity, impact strength, flexural strength, and flexural modulus, were tested according to the test methods described above. The results are shown in Table 2.

[0086] [Table 2]

[0087] As shown in Table 2, when novolac resin and 10 μm diameter glass fiber are used as raw materials, excellent processability, impact strength, flexural strength, and flexural modulus can be achieved as long as the L / D value requirement is met. Conversely, if the L / D value requirement is not met, the required impact strength, flexural strength, and flexural modulus cannot be achieved simultaneously.

[0088] 4.2.3. Examples 8-9 and Comparative Examples 10-11 [Example 8]

[0089] A resin composition was prepared by uniformly mixing 37 parts by weight of resol resin, 1.8 parts by weight of calcium hydroxide (Ca(OH)2), 1.5 parts by weight of reinforcing agent, 10.2 parts by weight of filler, 1.5 parts by weight of lubricant and release agent, 1.3 parts by weight of carbon black, 0.7 parts by weight of nitrogen-containing flame retardant compound, and 1.0 part by weight of ureidosilane coupling agent in a mixer for 20 minutes. Next, 45 parts by weight of glass fibers with a diameter of 7 μm and a length of 1.5 mm were added and mixed for 1 minute to form a premixed material.

[0090] The premixed material was fed into a two-roll mixer equipped with rollers measuring 8 inches in diameter and 24 inches in length. Mixing was carried out under the following conditions: the gap between the two rollers was set to 0.6 mm, the roller temperature was 90°C to 110°C, the roller rotation speed was 22 rpm, and the mixing time was 180 seconds. After mixing, the resulting phenolic resin composite product was cooled to room temperature and then crushed into particles.

[0091] [Example 9] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 8, except that the amounts of each component in the resin composition were adjusted to 31 parts by weight of novolak resin, 0.5 parts by weight of calcium hydroxide (Ca(OH)2), 6 parts by weight of hexamethylenetetramine, 1.0 part by weight of reinforcing agent, 10 parts by weight of filler, 1.5 parts by weight of carbon black, 0.6 parts by weight of ureidosilane coupling agent, and 50 parts by weight of glass fiber having a diameter of 7 μm and a length of 1.5 mm.

[0092] [Comparative Example 10] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 8, except that glass fibers having a diameter of 7 μm and a length of 3 mm were used instead of the glass fibers having a diameter of 7 μm and a length of 1.5 mm.

[0093] [Comparative Example 11] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 9, except that glass fibers having a diameter of 7 μm and a length of 3 mm were used instead of the glass fibers having a diameter of 7 μm and a length of 1.5 mm.

[0094] [Characteristics analysis] The properties of the phenolic resin composite materials of Examples 8 to 9 and Comparative Examples 10 to 11, including the L / D value of the glass fiber, apparent specific gravity, impact strength, flexural strength, and flexural modulus, were measured according to the test methods described above. The results are shown in Table 3.

[0095] [Table 3]

[0096] As shown in Table 3, when using 7 μm diameter glass fiber as the raw material, as long as the L / D value requirement is met, excellent processability, impact strength, flexural strength, and flexural modulus can be achieved. Conversely, if this requirement is not met, the required impact strength, flexural strength, and flexural modulus cannot be simultaneously achieved.

[0097] 4.2.4. Example 10 and Comparative Example 12 [Example 10] A resin composition was prepared by uniformly mixing 31 parts by weight of novolac resin, 0.5 parts by weight of calcium hydroxide (Ca(OH)2), 6 parts by weight of hexamethylenetetramine, 1.0 part by weight of reinforcing agent, 10 parts by weight of filler, 1.5 parts by weight of carbon black, and 0.6 parts by weight of ureidosilane coupling agent in a mixer for 20 minutes. Next, 50 parts by weight of glass fiber with a diameter of 13 μm and a length of 1.5 mm was added to the mixture and mixed for 1 minute to form a premixed material.

[0098] The premixed material was fed into a two-roll mixer equipped with rollers measuring 8 inches in diameter and 24 inches in length. Mixing was carried out under the following conditions: the gap between the two rollers was set to 0.6 mm, the roller temperature was 90°C to 110°C, the roller rotation speed was 22 rpm, and the mixing time was 180 seconds. After mixing, the resulting phenolic resin composite product was cooled to room temperature and then crushed into particles.

[0099] [Comparative Example 12] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 10, except that glass fibers having a diameter of 13 μm and a length of 3 mm were used instead of the glass fibers having a diameter of 13 μm and a length of 1.5 mm.

[0100] [Characteristics analysis] The properties of the phenolic resin composite materials of Example 10 and Comparative Example 12, including the L / D value of the glass fiber, apparent specific gravity, impact strength, flexural strength, and flexural modulus, were measured according to the test methods described above. The results are shown in Table 4.

[0101] [Table 4]

[0102] As shown in Table 4, when glass fibers with a diameter of 13 μm are used as raw materials, as long as the L / D value requirement is met, excellent processability, impact strength, flexural strength, and flexural modulus can be provided. Conversely, if this requirement is not met, the required impact strength, flexural strength, and flexural modulus cannot be simultaneously provided.

[0103] 4.2.5. Examples 11 to 15 and Reference Example 1 [Example 11] A resin composition was prepared by uniformly mixing 37 parts by weight of resole resin, 1.8 parts by weight of calcium hydroxide (Ca(OH)2), 1.5 parts by weight of reinforcing agent, 10.2 parts by weight of filler, 1.5 parts by weight of lubricant and release agent, 1.3 parts by weight of carbon black, 0.7 parts by weight of nitrogen-containing flame retardant compound, and 0.1 part by weight of ureidosilane coupling agent in a mixer for 20 minutes. Next, 45 parts by weight of glass fibers with a diameter of 10 μm and a length of 1.7 mm were added and mixed for 1 minute to form a premixed material.

[0104] The premixed material was fed into a two-roll mixer equipped with rollers measuring 8 inches in diameter and 24 inches in length. Mixing was carried out under the following conditions: the gap between the two rollers was set to 0.6 mm, the roller temperature was 90°C to 110°C, the roller rotation speed was 22 rpm, and the mixing time was 180 seconds. After mixing, the resulting phenolic resin composite product was cooled to room temperature and then crushed into particles.

[0105] [Example 12] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 11, except that the amount of the ureidosilane coupling agent was adjusted to 1.0 part by weight.

[0106] [Example 13] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 11, except that the amount of the ureidosilane coupling agent was adjusted to 1.5 parts by weight.

[0107] [Example 14] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 11, except that the amount of the ureidosilane coupling agent was adjusted to 2.0 parts by weight.

[0108] [Example 15] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 11, except that the amount of the ureidosilane coupling agent was adjusted to 3.0 parts by weight.

[0109] [Reference example 1] A phenolic resin composite material was prepared by repeating the preparation procedure of Example 12, except that an aminosilane coupling agent was used instead of the ureidosilane coupling agent.

[0110] [Characteristics analysis] The properties of the phenolic resin composite materials of Examples 11 to 15 and Reference Example 1, including the L / D value of the glass fiber, flexural strength, and flexural modulus, were measured according to the test methods described above. The results are shown in Table 5.

[0111] [Table 5]

[0112] As shown in Table 5, when an additional silane coupling agent was used in the phenolic resin composite material, Examples 11 to 15, which used a ureidosilane coupling agent, exhibited superior flexural strength and flexural modulus compared to Reference Example 1, which used an aminosilane coupling agent. Therefore, in the present invention, it is preferable to use an additional ureidosilane coupling agent.

[0113] The above examples explain the principle and effectiveness of the present application and show its inventive features. Those skilled in the art may make various modifications and substitutions based on the disclosure and suggestions of the present application described without departing from the principle. Therefore, the scope of protection of the present application is as defined in the appended claims.

Claims

1. A phenolic resin composite material comprising (A) a phenolic resin and (B) a glass fiber, The ratio (L / D) of the length L of the glass fiber (B) to the diameter D satisfies the following condition: Based on the total number of the glass fibers, 1.7% to 22.4% of the glass fibers have an L / D value of 5 to 10, 77% to 98.3% of the glass fibers have an L / D value greater than 10 and less than 100, and less than 1.4% of the glass fibers have an L / D value greater than 100; The phenolic resin composite material, wherein the length L and the diameter D are in μm.

2. 2. The phenolic resin composite material of claim 1, wherein 40% to 85% of the glass fibers have an L / D value of more than 10 and not more than 30, based on the total number of the glass fibers.

3. 2. The phenolic resin composite material of claim 1, wherein the diameter D of the glass fiber (B) is in the range of 6 μm to 14 μm.

4. 2. The phenolic resin composite material of claim 1, wherein the length L of the glass fiber (B) is in the range of 30 μm to 1700 μm.

5. 2. The phenolic resin composite material according to claim 1, wherein the glass fibers (B) have an average length of 100 μm to 400 μm.

6. 6. The phenolic resin composite material according to claim 1, wherein the amount of the glass fiber (B) is in the range of 30 parts by weight to 56 parts by weight, based on 100 parts by weight of the phenolic resin composite material.

7. 6. The phenolic resin composite material of claim 1, further comprising an additive selected from the group consisting of a silane coupling agent, carbon black, a filler, a cure accelerator, a lubricant, a mold release agent, a flame retardant, and combinations thereof.

8. The phenolic resin composite material according to claim 1 , further comprising a silane coupling agent.

9. 9. The phenolic resin composite material according to claim 8, wherein the amount of the silane coupling agent is in the range of 0.2 parts by weight to 7.0 parts by weight, based on 100 parts by weight of the glass fiber (B).

10. The phenolic resin composite material according to claim 8 , wherein the silane coupling agent is a ureidosilane coupling agent.

11. The phenolic resin composite further comprises carbon black; 6. The phenolic resin composite material of claim 1, wherein the amount of carbon black ranges from 1.0 parts by weight to 2.0 parts by weight, based on 100 parts by weight of the phenolic resin composite material.

12. The apparent specific gravity of the phenolic resin composite material is 0.64 g / cm 3 ~0.75g / cm 3 and The phenolic resin composite material according to claim 1 , wherein the apparent specific gravity is measured in accordance with JIS K6911.

13. A phenolic resin product produced from the phenolic resin composite material of any one of claims 1 to 5.

Images